CN102050722B - 4-biphenylsubstituted pyrazolidin-3,5-dione derivatives - Google Patents

4-biphenylsubstituted pyrazolidin-3,5-dione derivatives Download PDF

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CN102050722B
CN102050722B CN201010540066.1A CN201010540066A CN102050722B CN 102050722 B CN102050722 B CN 102050722B CN 201010540066 A CN201010540066 A CN 201010540066A CN 102050722 B CN102050722 B CN 102050722B
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alkyl
methyl
chlorine
represent
fluorine
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CN102050722A (en
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R·菲舍尔
T·布雷特施奈德
E·R·F·格兴
D·福伊希特
K-H·库克
P·勒塞尔
O·马萨姆
C·阿诺德
T·奥勒
M·J·希尔斯
H·科恩
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Bayer Pharma AG
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract

The invention relates to novel 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives, of formula (I), where A, D, G, W, X, Y and Z have the given meanings, several methods for production thereof and use thereof as pesticidal agent and/or as herbicide and/or as microbicide. The invention further relates to selective herbicidal agents comprising the 4-biphenyl-substituted pyrazolidin-3,5-dione derivatives of formula (I) and a compound improving the acceptability of the crop.

Description

Pyrazolidine-3 that 4-xenyl replaces, 5-derovatives
The application is to be on August 2nd, 2004 applying date, and application number is 200480029341.6, and denomination of invention is the dividing an application of application for a patent for invention of " pyrazolidine-3 that 4-xenyl replaces, 5-derovatives ".
The present invention relates to pyrazolidine-3 that novel 4-xenyl replaces, 5-derovatives, its multiple preparation method and as the purposes of sterilant and/or weedicide and/or microbicide.In addition, the invention still further relates to new selective weeding active compound binding substances (combination), described binding substances comprises pyrazolidine-3 that described 4-xenyl replaces, 5-derovatives improves the compound of farm crop tolerance with at least one, can be used for selectivity and prevent and treat the weeds in multiple beneficial plant crop, and can obtain particularly preferred effect.
4-arylpyrazole alkane-3 that there is weeding, kill mite and insecticidal properties, 5-derovatives in EP-A-508 126, WO 92,/16 150, WO 96/,721 652, WO 99,/43 649, WO 99,/47 525, WO 99,/48 869, WO 99,/55 673, WO 01,/17 351, WO 01,/17 352, WO 01,/17 353, WO 01,/17 972, WO 01,/17 973, WO 03/,062 244, WO 03/028446, have been narrated.Same known 4-arylpyrazole alkane in addition, has reported that this compounds has fungicidal properties (WO 96,/36 229, WO 96,/36 615, WO 96,/36 616, WO 96,/36 633).
Yet particularly, when low rate of application and lower concentration, effect and the action spectrum of these compounds are not always entirely satisfactory.And the plant tolerance of these compounds is also not always enough.
The invention provides new formula (I) compound
Wherein
X represents halogen, alkyl, alkoxyl group, alkene oxygen base, alkylthio, alkyl sulphinyl, alkyl sulphonyl, haloalkyl, halogenated alkoxy, haloalkene oxygen base, nitro, cyano group,
Z representative is optional aryl or the heteroaryl replacing separately,
W and Y represent hydrogen, halogen, alkyl, alkoxyl group, alkene oxygen base, haloalkyl, halogenated alkoxy, haloalkene oxygen base, nitro or cyano group independently of one another,
A representative is alkyl, thiazolinyl, alkoxyalkyl, the optional saturated cyclic alkyls replacing of optional halo separately,
D represents hydrogen, or represents alkyl, thiazolinyl or the alkoxyalkyl of optional halo separately,
Together with the atom that A is connected with them with D, represent saturated or undersaturated 6 or 7 rings, described ring optionally comprises at least one heteroatoms more in addition, and does not replace or replace in A, D part, or optional 5 rings that replace of representative,
G represents hydrogen (a), or represents one of following radicals
Wherein
E representation metal ion or ammonium,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R 1representative is alkyl, thiazolinyl, alkoxyalkyl, alkylthio alkyl, the multi-alkoxy alkyl of optional halo separately, or the cycloalkyl optionally being replaced by halogen, alkyl or alkoxyl group, described cycloalkyl can be by least one heteroatoms interval (interrupted), representative is optional phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or the heteroaryloxy alkyl replacing separately
R 2representative is alkyl, the thiazolinyl of optional halo separately, or represents optional cycloalkyl, phenyl or the benzyl replacing separately,
R 3, R 4and R 5represent independently of one another alkyl, alkoxyl group, alkylamino, dialkyl amido, alkylthio, the alkenylthio group of optional halo separately, cycloalkyl sulfenyl, or represent optional phenyl, benzyl, phenoxy group or the thiophenyl replacing separately, and
R 6and R 7represent independently of one another hydrogen, alkyl, cycloalkyl, thiazolinyl, alkoxyl group, the alkoxyalkyl of optional halo separately, the optional phenyl replacing of representative, the optional benzyl replacing of representative, or together with the N atom connecting with them, represent optionally by the ring at oxygen or sulphur interval.
In various character, the substituent character of Main Basis, formula (I) compound can how much and/or the form of optical isomer exist, or the isomer mixture form forming with difference exists, can be separated by conventional methods if described mixture is suitable.The invention provides pure isomer and isomer mixture, and its production and use, and the composition that comprises them.Yet, for simplicity, hereinafter only claim formula (I) compound, but its implication had both referred to pure compound, if the suitable mixture that also refers to the isomer of different ratios.
According to the position of substituting group G, formula (I) compound can formula (I-A) and two kinds of isomeric forms of formula (I-B) exist,
Described two kinds of isomeric forms represent with the dotted line in formula (I).
Formula (I-A) and formula (I-B) compound both can mixture also can its pure isomer form exist.The mixture of formula (I-A) and formula (I-B) compound, can pass through physical method for separation in known manner if suitable, for example, pass through chromatographic process.
For clarity sake, hereinafter only express separately a kind of in may isomer.This does not get rid of, if the suitable form that can isomer mixture of compound exists, or exists with corresponding other isomeric forms.
By the different implications (a) of group G, (b), (c), (d), (e), (f) with (g), comprise wherein, obtain following basic structure (I-a) to (I-g),
Wherein
A, D, E, L, M, W, X, Y, Z, R 1, R 2, R 3, R 4, R 5, R 6, R 7definition as above.
(A) 3-hydroxy-4-phenyl-5-oxopyrazoline or its diketone of the replacement of discoverable type (I-a) make by following reaction,
Wherein
A, D, W, X, Y and Z define as above:
If (α) be suitably under the existence of thinner, and if be suitably under the existence of alkali, the halo chloro carbonyl ketone of formula (II) and the hydrazine reaction of formula (IV),
Wherein
W, X, Y and Z definition are as above
And
Hal represents halogen (particularly chlorine or bromine)
Or
If (β) be suitably under the existence of thinner, and if be suitably under the existence of alkali, the hydrazine reaction of the malonate derivative of formula (III) and formula (IV),
Wherein
W, X, Y and Z define as above, and
U represents NH 2or C 1-C 8alkoxyl group
A-NH-NH-D (IV)
Wherein
A and D define as above,
Or
If (γ) be suitably under the existence of thinner, and if be suitably under the existence of alkali, formula (V) compound reacts
Wherein
A, D, W, X, Y and Z define as above, and
R 8represent C 1-C 8alkyl.
(B) in addition, above formula shown (I-a) makes by following reaction to formula (I-g) compound, its Chinese style (I-a) to A, the D of formula (I-g), G, W, X, Y and Z definition as above:
Under the existence of solvent, alkali and catalyzer, formula (I '-a) to the acid reaction of formula (I '-g) compound and formula (VI), wherein applicable catalyzer is, particularly palladium complex
Wherein
A, D, G, W, X and Y define as above, and
Z ' represents chlorine, bromine, iodine, preferred chlorine,
Wherein
Z definition as above.
And, found following (C) to (I):
(C) above formula shown (I-b) compound makes by following reaction, A, D, the R of its Chinese style (I-b) 1, W, X, Y and Z definition as above:
If (α) be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with the carboxylic acid halides of formula (VII), A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
Wherein
R 1define as above, and
Hal represents halogen (particularly chlorine or bromine)
Or
If (β) be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, the anhydride reaction of formula shown (I-a) compound and formula (VIII) above, A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
R 1-CO-O-CO-R 1 (VIII)
Wherein
R 1definition as above;
(D) above formula shown (I-c) compound makes by following reaction, A, D, the R of its Chinese style (I-c) 2, M, W, X, Y and Z definition as above, and L represents oxygen:
If be suitably under the existence of thinner, if and be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with chloro-formic ester or the chloroformic acid thioesters of formula (IX) respectively, and A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
R 2-M-CO-Cl (IX)
Wherein
R 2define as above with M;
(E) above formula shown (I-c) compound makes by following reaction, A, D, the R of its Chinese style (I-c) 2, M, W, X, Y and Z definition as above, and L represents sulphur:
If be suitably under the existence of thinner, if and be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with chloro list thiocarboxylic or the chloro dithio formate of formula (X) respectively, and A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
Wherein
M and R 2define as above,
And
(F) above formula shown (I-d) compound makes by following reaction, A, D, the R of its Chinese style (I-d) 3, W, X, Y and Z definition as above:
If be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with the SULPHURYL CHLORIDE of formula (XI) respectively, A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
R 3-SO 2-Cl (XI)
Wherein
R 3define as above,
(G) above formula shown (I-e) compound makes by following reaction, A, D, L, the R of its Chinese style (I-e) 4, R 5, W, X, Y and Z definition as above:
If be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with the P contained compound of formula (XII) respectively, A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
Wherein
L, R 4and R 5define as above, and
Hal represents halogen (particularly chlorine or bromine),
(H) above formula shown (I-f) compound makes by following reaction, and A, the D of its Chinese style (I-f), E, W, X, Y and Z define as above:
If be suitably under the existence of thinner, above formula shown (I-a) compound reacts with the metallic compound of formula (X III) or the amine of formula (X IV) respectively correspondingly, and A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
Me(OR 9) 1(XIII)
Wherein
Me represents monovalence or divalent metal (preferred as alkali or alkaline-earth metal, for example lithium, sodium, potassium, magnesium or calcium),
T represents numeral 1 or 2, and
R 9, R 10, R 11, R 12represent independently of one another hydrogen or alkyl (preferred C 1-C 8alkyl),
(I) above formula shown (I-g) compound makes by following reaction, A, D, L, the R of its Chinese style (I-g) 6, R 7, W, X, Y and Z definition as above:
If (α) be suitably under the existence of thinner, if and be suitably under the existence of catalyzer, above formula shown (I-a) compound reacts with isocyanic ester or the lsothiocyanates of formula (X V) respectively, and A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
R 6-N＝C＝L (XV)
Wherein
R 6define as above with L,
Or
If (β) be suitably under the existence of thinner, if and be suitably under the existence of acid binding agent, above formula shown (I-a) compound reacts with urea chloride or the thiocarbamyl chlorine of formula (X VI) respectively, and A, the D of its Chinese style (I-a), W, X, Y and Z definition are as above
Wherein
L, R 6and R 7definition as above.
And, found that new formula (I) compound is very effective sterilant, preferably insecticide and/or acarus-killing and/or weedicide.
Surprisingly, have now found that pyrazolidine-3 that some 4-xenyl replaces, 5-derovatives, when using together with the following compound (safener/toxinicide) that improves farm crop tolerance, can very effectively prevent the destruction to farm crop, and can particularly advantageously be used as wide spectrum conjugate preparations, for the undesired plant of selectivity control useful plants crop, described useful plants such as grain, and corn, soybean and paddy rice.
The present invention also provides the selective herbicidal composition that comprises significant quantity active agent combinations, and described binding substances comprises following component:
Pyrazolidine-3 that the 4-xenyl of (a ') at least one formula (I) replaces, 5-derovatives, wherein A, D, G, W, X, Y and Z definition are as above
With
At least one is selected from the following compound that improves farm crop tolerance (b '):
4-dichloro-acetyl-1-oxa--4-azaspiro [4.5] decane (AD-67, MON-4660),
1-dichloro-acetyl six hydrogen-3,3,8a-trimethylammonium pyrrolo-[1,2-a] pyrimidine-6 (2H)-one (dicyclonon, BAS-145138),
4-dichloro-acetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benoxacor (benoxacor)),
The own ester of 5-chloroquinoline-8-ethoxyacetic acid-1-methyl (cloquitocet_mexyl (cloquintocet-mexyl), referring to related compound in EP-A-86750, EP-A-94349, EP-A-191736, EP-A-492366),
3-(2-chlorophenylmethyl)-1-(1-methyl isophthalic acid-styroyl) urea (cumyluron (cumyluron)),
α-(cyano group methoxyimino) benzyl cyanide (cyometrinil (cyometrinil)),
2,4 dichloro benzene ethoxyacetic acid (2,4-D),
4-(2,4 dichloro benzene oxygen base) butyric acid (2,4-DB),
1-(1-methyl isophthalic acid-phenylethyl)-3-(4-aminomethyl phenyl) urea (daimuron (daimuron, dymron)),
The chloro-O-Anisic Acid of 3,6-bis-(dicamba 98 (dicamba)),
Piperidines-1-thiocarboxylic acid-S-1-methyl isophthalic acid-phenyl chlorocarbonate (dimepiperate (dimepiperate)),
The chloro-N-of 2,2-bis-(2-oxo-2-(2-propenyl is amino) ethyl)-N-(2-propenyl) ethanamide (DKA-24),
The chloro-N of 2,2-bis-, N-bis--2-propenyl ethanamide (dichlormide (dichlormid)),
The chloro-2-phenyl pyrimidine of 4,6-bis-(fenclorim (fenclorim)),
1-(2,4 dichloro benzene base)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylic acid, ethyl ester (fenchlorazole-ethyl, referring to related compound in EP-A-174562 and EP-A-346620),
The chloro-4-trifluoromethyl thiazole-5-of 2-carboxylic acid benzene methyl (separating careless amine (flurazole)),
The chloro-N-of 4-(DOX-2-base-methoxyl group)-α-trifluoroacetyl benzophenone oxime (fluxofenim (fluxofenim)),
3-dichloro-acetyl-5-(2-furyl)-2,2-bis-Jia Ji oxazolidine (Xie Cao oxazole (furilazole), MON-13900),
4,5-dihydro-5,5-phenylbenzene-3-isoxazole carboxylic acid, ethyl ester (isoxadifen-ethyl, referring to related compound in WO-A-95/07897),
Chloro-O-Anisic Acid-the 1-of 3,6-bis-(ethoxy carbonyl) ethyl ester (lactidichlor),
(the chloro-o-tolyloxy of 4-) acetic acid (MCPA),
2-(the chloro-o-tolyloxy of 4-) propionic acid (Vi par (mecoprop)),
1-(2,4 dichloro benzene base)-4,5-dihydro-5-methyl isophthalic acid H-pyrazoles-3,5-diethyl dicarboxylate (mefenpyrdiethyl (mefenpyr-diethyl), referring to related compound in WO-A-91/07874),
2-dichloromethyl-2-methyl isophthalic acid, 3-dioxolane alkane (MG-191),
2-propenyl-1-oxa--4-azaspiro [4.5] decane-4-dithiocarboxylic esters (MG-838),
1,8-naphthalic anhydride,
α-(DOX-2-base-methoxyimino) benzyl cyanide (oxabetrinil (oxabetrinil)),
The chloro-N-of 2,2-bis-(DOX-2-base-methyl)-N-(2-propenyl) ethanamide (PPG-1292),
3-dichloro-acetyl-2,2-bis-Jia Ji oxazolidine (R-28725),
3-dichloro-acetyl-2,2,5-tri-Jia Ji oxazolidine (R-29148),
4-(the chloro-o-tolyl of 4-) butyric acid,
4-(4-chlorophenoxy) butyric acid,
Diphenylmethyl ethoxyacetic acid,
Phenylbenzene methoxy menthyl acetate,
Diphenylmethyl ethoxyacetic acid ethyl ester,
1-(2-chloro-phenyl-)-5-phenyl-1H-pyrazoles-3-carboxylate methyl ester,
1-(2,4 dichloro benzene base)-5-methyl isophthalic acid H-pyrazoles-3-carboxylic acid, ethyl ester,
1-(2,4 dichloro benzene base)-5-sec.-propyl-1H-pyrazoles-3-carboxylic acid, ethyl ester,
1-(2,4 dichloro benzene base)-5-(1,1-dimethyl ethyl)-1H-pyrazoles-3-carboxylic acid, ethyl ester,
1-(2,4 dichloro benzene base)-5-phenyl-1H-pyrazoles-3-carboxylic acid, ethyl ester (referring to related compound in EP-A-269806 and EP-A-333131),
5-(2,4 dichloro benzene methyl)-2-isoxazoline-3-carboxylic acid, ethyl ester,
5-phenyl-2-isoxazoline-3-carboxylic acid, ethyl ester,
5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid, ethyl ester (referring to related compound in WO-A-91/08202),
5-chloroquinoline-8-ethoxyacetic acid-1,3-dimethyl butyrate-1-base ester,
5-chloroquinoline-8-ethoxyacetic acid-4-allyloxy butyl ester,
5-chloroquinoline-8-ethoxyacetic acid-1-allyloxy third-2-base ester,
5-chloro-quinoxaline-8-ethoxyacetic acid methyl esters,
5-chloroquinoline-8-ethoxyacetic acid ethyl ester,
5-chloro-quinoxaline-8-ethoxyacetic acid allyl ester,
5-chloroquinoline-8-ethoxyacetic acid-2-oxo third-1-base ester,
5-chloroquinoline-8-oxygen propylmalonic acid diethyl ester,
5-chloro-quinoxaline-8-oxygen propylmalonic acid diallyl,
5-chloroquinoline-8-oxygen propylmalonic acid diethyl ester (referring to related compound in EP-A-582198),
4-carboxyl chroman-4-guanidine-acetic acid (AC-304415, referring to EP-A-613618),
4-chlorophenoxyacetic acid,
3,3 '-dimethyl-4-methoxyl group benzophenone,
The bromo-4-chloromethyl of 1-alkylsulfonyl benzene,
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3-MU (being N-(2-anisoyl)-4-[(methylamino carbonyl) amino] benzsulfamide),
1-[4-(N-2-anisoyl sulfamyl) phenyl]-3,3-dimethyl urea,
1-[4-(N-4,5-dimethylbenzoyl sulfamyl) phenyl]-3-MU,
1-[4-(N-naphthyl sulfamyl) phenyl]-3,3-dimethyl urea,
N-(2-methoxyl group-5-methyl benzoyl)-4-(cyclopropylamino carbonyl) benzsulfamide,
One of and/or the following compound being defined by general formula,
(II a) for general formula
Or general formula (II b)
Or general formula (II c)
Wherein
N represents the numeral between 0 to 5,
A 1represent one of divalent heterocyclic group shown below
N represents the numeral between 0 to 5,
A 2representative is optionally by C 1-C 4alkyl and/or C 1-C 4two bases of the alkane with 1 or 2 carbon atom that alkoxy carbonyl replaces,
R 21representation hydroxy, sulfydryl, amino, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkylamino or two-(C 1-C 4alkyl) amino,
R 22representation hydroxy, sulfydryl, amino, C 1-C 6alkoxyl group, C 1-C 8alkene oxygen base, C 1-C 6alkylthio, C 1-C 6alkylamino or two-(C 1-C 4alkyl) amino,
R 23the C that representative is optionally replaced by fluorine, chlorine and/or bromine separately 1-C 4alkyl,
R 24represent hydrogen, the C optionally being replaced by fluorine, chlorine and/or bromine separately 1-C 6alkyl, C 2-C 6thiazolinyl or C 2-C 6alkynyl, C 1-C 4alkoxy-C 1-C 4alkyl, dioxolanyl-C 1-C 4alkyl, furyl, furyl-C 1-C 4alkyl, thienyl, thiazolyl, piperidyl or optionally by fluorine, chlorine and/or bromine or C 1-C 4the phenyl that alkyl replaces,
R 25represent hydrogen, the C optionally being replaced by fluorine, chlorine and/or bromine separately 1-C 6alkyl, C 2-C 6thiazolinyl or C 2-C 6alkynyl, C 1-C 4alkoxy-C 1-C 4alkyl, dioxolanyl-C 1-C 4alkyl, furyl, furyl-C 1-C 4alkyl, thienyl, thiazolyl, piperidyl or optionally by fluorine, chlorine and/or bromine or C 1-C 4the phenyl that alkyl replaces, or and R 24representative is separately optionally by C together 1-C 4alkyl, phenyl, furyl, fused benzene rings or the C being replaced by two substituting groups 3-C 6alkane two bases or C 2-C 5oxa-alkane two bases, form 5 or 6 yuan of carbocyclic rings together with the C atom that described two substituting groups connect with them,
R 26represent hydrogen, cyano group, halogen, or representative is separately optionally by the C of fluorine, chlorine and/or bromine replacement 1-C 4alkyl, C 3-C 6cycloalkyl or phenyl,
R 27represent hydrogen, optionally by hydroxyl, cyano group, halogen or C 1-C 4the C that alkoxyl group replaces 1-C 6alkyl, C 3-C 6cycloalkyl or three-(C 1-C 4alkyl) silyl,
R 28represent hydrogen, cyano group, halogen, or representative is separately optionally by the C of fluorine, chlorine and/or bromine replacement 1-C 4alkyl, C 3-C 6cycloalkyl or phenyl,
X 1represent nitro, cyano group, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4halogenated alkoxy,
X 2represent hydrogen, cyano group, nitro, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4halogenated alkoxy,
X 3represent hydrogen, cyano group, nitro, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4halogenated alkoxy,
And/or the following compound being defined by general formula,
General formula (II d)
Or general formula (II e)
Wherein
N represents the numeral between 0 to 5,
R 29represent hydrogen or C 1-C 4alkyl,
R 30represent hydrogen or C 1-C 4alkyl,
R 31represent hydrogen, separately optionally by cyano group, halogen or C 1-C 4the C that alkoxyl group replaces 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkylamino or two-(C 1-C 4alkyl) amino or separately optionally by cyano group, halogen or C 1-C 4the C that alkyl replaces 3-C 6cycloalkyl, C 3-C 6cycloalkyl oxy, C 3-C 6cycloalkyl sulfenyl or C 3-C 6cycloalkyl amino,
R 32represent hydrogen, optionally by cyano group, hydroxyl, halogen or C 1-C 4the C that alkoxyl group replaces 1-C 6alkyl, the C optionally being replaced by cyano group or halogen separately 3-C 6thiazolinyl or C 3-C 6alkynyl or optionally by cyano group, halogen or C 1-C 4the C that alkyl replaces 3-C 6cycloalkyl,
R 33represent hydrogen, optionally by cyano group, hydroxyl, halogen or C 1-C 4the C that alkoxyl group replaces 1-C 6alkyl, the C optionally being replaced by cyano group or halogen separately 3-C 6thiazolinyl or C 3-C 6alkynyl, optionally by cyano group, halogen or C 1-C 4the C that alkyl replaces 3-C 6cycloalkyl or optionally by nitro, cyano group, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4the phenyl that halogenated alkoxy replaces, or and R 32representative is separately optionally by C together 1-C 4the C that alkyl replaces 2-C 6alkane two bases or C 2-C 5oxa-alkane two bases,
X 4represent nitro, cyano group, carboxyl, formamyl, formyl radical, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4halogenated alkoxy, and
X 5represent nitro, cyano group, carboxyl, formamyl, formyl radical, amino-sulfonyl, hydroxyl, amino, halogen, C 1-C 4alkyl, C 1-C 4haloalkyl, C 1-C 4alkoxyl group or C 1-C 4halogenated alkoxy.
Formula (I) provides the General Definition of the compounds of this invention.Preferred substituents or group range above and in the structural formula of mentioning are below set forth as follows:
X preferably represents halogen, C 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl group, C 3-C 6alkene oxygen base, C 1-C 6alkylthio, C 1-C 6alkyl sulphinyl, C 1-C 6alkyl sulphonyl, C 1-C 6halogenated alkoxy, C 3-C 6haloalkene oxygen base, nitro or cyano group,
W and Y preferably represent hydrogen, halogen, C independently of one another 1-C 6alkyl, C 1-C 6haloalkyl, C 1-C 6alkoxyl group, C 1-C 6halogenated alkoxy, nitro or cyano group,
Z preferably represents one of following radicals
V 1preferably represent halogen, C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphinyl, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro, cyano group, or representative is separately optionally by halogen, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or cyano group list or polysubstituted phenyl, phenoxy group, phenoxy group-C 1-C 4alkyl, phenyl-C 1-C 4alkoxyl group, thiophenyl-C 1-C 4alkyl or phenyl-C 1-C 4alkylthio,
V 2and V 3preferably represent independently of one another hydrogen, halogen, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 4haloalkyl or C 1-C 4halogenated alkoxy,
A preferably represents the C of optional halo separately 1-C 8alkyl, C 3-C 8thiazolinyl or optionally by C 1-C 4alkyl, halogen or C 1-C 4the C that alkoxyl group replaces 3-C 6cycloalkyl,
D preferably represents hydrogen, and representative is the C of optional halo separately 1-C 8alkyl or C 3-C 8thiazolinyl,
The A C that preferably representative optionally replaces separately together with D 4-C 6alkane two bases or C 4-C 6alkene two bases, wherein an optional methylene radical can be replaced by oxygen or sulphur,
Possible substituting group is respectively:
Halogen, hydroxyl, sulfydryl or the separately C of optional halo 1-C 10alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 3-C 7cycloalkyl, phenyl, benzyloxy or another C 1-C 6alkane two bases,
Or optionally comprise one of following radicals
Or preferably representative is optionally by halogen, C 1-C 6alkyl, C 1-C 4haloalkyl or C 1-C 6alkoxyl group one is to trisubstituted C 3alkane two bases,
G preferably represents hydrogen (a), or represents one of following radicals
particularly (a), (b) or (c),
Wherein
E representation metal ion or ammonium ion,
L represents oxygen or sulphur, and
M represents oxygen or sulphur,
R 1preferably represent the C of optional halo separately 1-C 20alkyl, C 2-C 20thiazolinyl, C 1-C 8alkoxy-C 1-C 8alkyl, C 1-C 8alkylthio-C 1-C 8alkyl, many C 1-C 8alkoxy-C 1-C 8alkyl or optionally by halogen, C 1-C 6alkyl or C 1-C 6the C that alkoxyl group replaces 3-C 8cycloalkyl, in described cycloalkyl optionally one or more (being preferably no more than two) not the annular atoms of direct neighbor by oxygen and/or sulphur, replaced,
Representative is optionally by halogen, cyano group, nitro, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 6haloalkyl, C 1-C 6halogenated alkoxy, C 1-C 6alkylthio or C 1-C 6the phenyl that alkyl sulphonyl replaces,
Representative is optionally by halogen, nitro, cyano group, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 6haloalkyl or C 1-C 6phenyl-C that halogenated alkoxy replaces 1-C 6alkyl,
Representative is optionally by halogen or C 1-C 65 or 6 yuan of heteroaryls (for example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furyl or thienyl) that alkyl replaces,
Representative is optionally by halogen or C 1-C 6phenoxy group-C that alkyl replaces 1-C 6alkyl, or
Representative is separately optionally by halogen, amino or C 1-C 6alkyl replaces 5or 6the heteroaryl oxygen base-C of unit 1-C 6alkyl (pyridyl oxygen base-C for example 1-C 6alkyl, pyrimidyl oxygen base-C 1-C 6alkyl or thiazolyl oxygen base-C 1-C 6alkyl),
R 2preferably represent the C of optional halo separately 1-C 20alkyl, C 2-C 20thiazolinyl, C 1-C 8alkoxy-C 2-C 8alkyl, many C 1-C 8alkoxy-C 2-C 8alkyl,
Representative is optionally by halogen, C 1-C 6alkyl or C 1-C 6the C that alkoxyl group replaces 3-C 8cycloalkyl, or
Representative is separately optionally by halogen, cyano group, nitro, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 6haloalkyl or C 1-C 6phenyl or benzyl that halogenated alkoxy replaces,
R 3preferably represent the C of optional halo 1-C 8alkyl, or representative is separately optionally by halogen, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 4haloalkyl, C 1-C 4phenyl or benzyl that halogenated alkoxy, cyano group or nitro replace,
R 4and R 5preferably represent independently of one another the C of optional halo separately 1-C 8alkyl, C 1-C 8alkoxyl group, C 1-C 8alkylamino, two-(C 1-C 8alkyl) amino, C 1-C 8alkylthio, C 2-C 8alkenylthio group, C 3-C 7cycloalkyl sulfenyl, or representative is separately optionally by halogen, nitro, cyano group, C 1-C 4alkoxyl group, C 1-C 4halogenated alkoxy, C 1-C 4alkylthio, C 1-C 4halogenated alkylthio, C 1-C 4alkyl or C 1-C 4phenyl, phenoxy group or thiophenyl that haloalkyl replaces,
R 6and R 7preferably represent independently of one another hydrogen, representative is the C of optional halo separately 1-C 8alkyl, C 3-C 8cycloalkyl, C 1-C 8alkoxyl group, C 3-C 8thiazolinyl, C 1-C 8alkoxy-C 1-C 8alkyl, representative is optionally by halogen, C 1-C 8haloalkyl, C 1-C 8alkyl or C 1-C 8the phenyl that alkoxyl group replaces, representative is optionally by halogen, C 1-C 8alkyl, C 1-C 8haloalkyl or C 1-C 8the benzyl that alkoxyl group replaces, or represent optionally by C together 1-C 4the C that alkyl replaces 3-C 6alkylidene group, in described alkylidene group, an optional methylene radical is replaced by oxygen or sulphur,
R 13preferably represent hydrogen, representative is the C of optional halo separately 1-C 8alkyl or C 1-C 8alkoxyl group, representative is optionally by halogen, C 1-C 4alkyl or C 1-C 4the C that alkoxyl group replaces 3-C 8cycloalkyl, in described cycloalkyl, an optional methylene radical is replaced by oxygen or sulphur, or representative is separately optionally by halogen, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 4haloalkyl, C 1-C 4phenyl, phenyl-C that halogenated alkoxy, nitro or cyano group replace 1-C 4alkyl or phenyl-C 1-C 4alkoxyl group,
R 14preferably represent hydrogen or C 1-C 8alkyl, or
R 13and R 14preferably represent together C 4-C 6alkane two bases,
R 15and R 16identical or different, and preferably represent C 1-C 6alkyl, or
R 15and R 16preferably represent optionally by C together 1-C 6alkyl, C 1-C 6the C that haloalkyl replaces or is substituted by phenyl 2-C 4alkane two bases, described phenyl is optionally by halogen, C 1-C 6alkyl, C 1-C 4haloalkyl, C 1-C 6alkoxyl group, C 1-C 4halogenated alkoxy, nitro or cyano group replace,
R 17and R 18preferably represent independently of one another hydrogen, represent the C of optional halo 1-C 8alkyl, or representative is optionally by halogen, C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 4haloalkyl, C 1-C 4the phenyl that halogenated alkoxy, nitro or cyano group replace, or
R 17and R 18together with the carbon atom connecting with them, preferably represent carbonyl, or representative is optionally by halogen, C 1-C 4alkyl or C 1-C 4the C that alkoxyl group replaces 5-C 7cycloalkyl, in described cycloalkyl, an optional methylene radical is replaced by oxygen or sulphur,
R 19and R 20preferably represent independently of one another C 1-C 10alkyl, C 2-C 10thiazolinyl, C 1-C 10alkoxyl group, C 1-C 10alkylamino, C 3-C 10alkenyl amino, two-(C 1-C 10alkyl) amino or two-(C 3-C 10thiazolinyl) amino.
In the group definition as preferably proposing, halogen represents fluorine, chlorine, bromine and iodine, particularly fluorine, chlorine and bromine.
W more preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy,
X more preferably represents fluorine, chlorine, bromine, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 3-C 4alkene oxygen base, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, C 3-C 4haloalkene oxygen base, nitro or cyano group,
Y more preferably represents hydrogen, fluorine, chlorine, bromine, C 1-C 4alkyl, C 1-C 2haloalkyl, C 1-C 4alkoxyl group or C 1-C 2halogenated alkoxy,
Z more preferably represents one of following radicals
V 1more preferably represent fluorine, chlorine, bromine, C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro, cyano group, or representative is separately optionally by fluorine, chlorine, bromine, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or cyano group one or dibasic phenyl, phenoxy group, phenoxy group-C 1-C 2alkyl, phenyl-C 1-C 2alkoxyl group, thiophenyl-C 1-C 2alkyl or phenyl-C 1-C 2alkylthio,
V 2and V 3more preferably represent independently of one another hydrogen, fluorine, chlorine, bromine, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 2haloalkyl or C 1-C 2halogenated alkoxy,
A more preferably represents C 1-C 6alkyl, C 3-C 6thiazolinyl or C 3-C 6cycloalkyl,
D more preferably represents hydrogen, C 1-C 6alkyl or C 3-C 6thiazolinyl,
The A C that more preferably representative optionally replaces together with D 4-C 5alkane two bases, wherein an optional methylene radical can be replaced by carbonyl, oxygen or sulphur, and possible substituting group is hydroxyl, C 1-C 6alkyl, C 1-C 4alkoxyl group or another C 1-C 4alkane two bases, or
Optionally comprise one of following radicals
Or representative is optionally by fluorine, chlorine, trifluoromethyl, methyl, ethyl or methoxyl group one or dibasic C 3alkane two bases,
G more preferably represents hydrogen (a) or represents one of following radicals
particularly (a), (b) or (c),
Wherein
E representation metal ion or ammonium ion,
L represents oxygen or sulphur, and
M represents oxygen or sulphur,
R 1more preferably representative separately optionally by fluorine or chlorine one to trisubstituted C 1-C 8alkyl, C 2-C 8thiazolinyl, C 1-C 4alkoxy-C 1-C 2alkyl, C 1-C 4alkylthio-C 1-C 2alkyl, or representative is optionally by fluorine, chlorine, C 1-C 2alkyl or C 1-C 2alkoxyl group one or dibasic C 3-C 6cycloalkyl, in described cycloalkyl optional one or two not the annular atoms of direct neighbor by oxygen, replaced,
Representative is optionally by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 2haloalkyl or C 1-C 2halogenated alkoxy one or dibasic phenyl,
R 2more preferably representative separately optionally by fluorine one to trisubstituted C 1-C 8alkyl, C 2-C 8thiazolinyl or C 1-C 4alkoxy-C 2-C 4alkyl,
Representative is optionally by C 1-C 2alkyl or C 1-C 2the monobasic C of alkoxyl group 3-C 6cycloalkyl, or
Representative is separately optionally by fluorine, chlorine, bromine, cyano group, nitro, C 1-C 4alkyl, C 1-C 3alkoxyl group, trifluoromethyl or trifluoromethoxy one or dibasic phenyl or benzyl,
R 3more preferably representative optionally by fluorine one to trisubstituted C 1-C 6alkyl, or representative is separately optionally by fluorine, chlorine, bromine, C 1-C 4alkyl, C 1-C 4the monobasic phenyl of alkoxyl group, trifluoromethyl, trifluoromethoxy, cyano group or nitro or benzyl,
R 4more preferably representative separately optionally by fluorine one to trisubstituted C 1-C 6alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylamino, two-(C 1-C 6alkyl) amino, C 1-C 6alkylthio, C 3-C 4alkenylthio group, C 3-C 6cycloalkyl sulfenyl, or representative is separately optionally by fluorine, chlorine, bromine, nitro, cyano group, C 1-C 3alkoxyl group, C 1-C 3halogenated alkoxy, C 1-C 3alkylthio, C 1-C 3halogenated alkylthio, C 1-C 3alkyl or trifluoromethyl one or dibasic phenyl, phenoxy group or thiophenyl,
R 5more preferably represent C 1-C 6alkoxyl group or C 1-C 6alkylthio,
R 6more preferably represent hydrogen, representative separately optionally by fluorine one to trisubstituted C 1-C 6alkyl, C 3-C 6cycloalkyl, C 1-C 6alkoxyl group, C 3-C 6thiazolinyl, C 1-C 6alkoxy-C 1-C 4alkyl, representative is optionally by fluorine, chlorine, bromine, trifluoromethyl, C 1-C 4alkyl or C 1-C 4alkoxyl group one or dibasic phenyl, representative is optionally by fluorine, chlorine, bromine, C 1-C 4alkyl, trifluoromethyl or C 1-C 4the monobasic benzyl of alkoxyl group,
R 7more preferably represent C 1-C 6alkyl, C 3-C 6thiazolinyl or C 1-C 6alkoxy-C 1-C 4alkyl,
R 6and R 7more preferably represent optionally by methyl or ethyl one or dibasic C together 4-C 5alkylidene group, in described alkylidene group, an optional methylene radical is replaced by oxygen or sulphur,
R 15and R 16identical, and more preferably represent C 1-C 4alkyl,
R 15and R 16more preferably represent optionally by methyl, ethyl, propyl group or sec.-propyl one or dibasic C together 2-C 3alkane two bases,
R 17and R 18more preferably represent independently of one another hydrogen, representative separately optionally by fluorine and/or chlorine one to trisubstituted methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl, or
R 17and R 18together with the carbon atom connecting with them, more preferably represent carbonyl, or representative is optionally by the C of methyl, ethyl, methoxy or ethoxy replacement 5-C 6cycloalkyl, in described cycloalkyl, an optional methylene radical is replaced by oxygen.
In the group definition as more preferably proposing, halogen represents fluorine, chlorine, bromine and iodine, particularly fluorine, chlorine and bromine.
W most preferably represents hydrogen, methyl, ethyl or chlorine,
X most preferably represents chlorine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-or trifluoromethyl,
Y most preferably represents hydrogen, chlorine or methyl,
Z most preferably represents one of following radicals
Particularly (be equal to ),
V 1most preferably represent fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group, nitro or cyano group,
V 2and V 3most preferably represent independently of one another hydrogen, fluorine, chlorine, methyl, methoxyl group or trifluoromethyl,
A is represent methylidene, ethyl, propyl group or butyl most preferably,
D most preferably represents hydrogen, methyl or ethyl,
The A C that most preferably representative optionally replaces together with D 4-C 5alkane two bases, in described alkane two bases, an optional methylene radical is replaced by oxygen or sulphur, and described alkane two bases are optionally by hydroxyl, methyl, ethyl, methoxyl group, oxyethyl group or another C 1-C 4alkane two bases replace, or representative is optionally by fluorine, methyl, trifluoromethyl or methoxyl group one or dibasic C 3alkane two bases,
G most preferably represents hydrogen (a) or represents one of following radicals
-SO 2-R 3 (d)，
Particularly (a), (b) or (c)
Wherein
E representation metal ion equivalent or ammonium ion,
L represents oxygen or sulphur, and
M represents oxygen or sulphur,
R 1most preferably representative separately optionally by fluorine one to trisubstituted C 1-C 6alkyl, C 2-C 6thiazolinyl, C 1-C 2alkoxy-C 1alkyl, C 1-C 2alkylthio-C 1alkyl, or represent separately optionally by fluorine, chlorine, the monobasic cyclopropyl of methyl or methoxy or cyclohexyl,
Represent optionally by the monobasic phenyl of fluorine, chlorine, bromine, cyano group, nitro, methyl, methoxyl group, trifluoromethyl or trifluoromethoxy,
R 2most preferably representative is separately optionally by the monobasic C of fluorine 1-C 8alkyl, C 2-C 6thiazolinyl or C 1-C 4alkoxy-C 2-C 3alkyl,
Or represent separately optionally by the monobasic phenyl of fluorine, chlorine, cyano group, nitro, methyl, ethyl, n-propyl, sec.-propyl, methoxyl group, oxyethyl group, trifluoromethyl or trifluoromethoxy or benzyl,
R 3most preferably representative separately optionally by fluorine one to trisubstituted methyl, ethyl, n-propyl, sec.-propyl, or representative is separately optionally by the monobasic phenyl of fluorine, chlorine, bromine, methyl, the tertiary butyl, methoxyl group, trifluoromethyl, trifluoromethoxy, cyano group or nitro or benzyl
R 4most preferably representative separately optionally by fluorine one to trisubstituted C 1-C 4alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylamino, two-(C 1-C 4alkyl) amino, C 1-C 4alkylthio, or representative is separately optionally by fluorine, chlorine, bromine, nitro, cyano group, C 1-C 2alkoxyl group, C 1-C 2fluoroalkyl, C 1-C 2alkylthio, C 1-C 2fluoroalkane sulfenyl or C 1-C 3the monobasic phenyl of alkyl, phenoxy group or thiophenyl,
R 5most preferably representation methoxy, oxyethyl group, propoxy-, butoxy, methylthio group, ethylmercapto group, rosickyite base or butylthio,
R 6most preferably represent hydrogen, representative separately optionally by fluorine one to trisubstituted C 1-C 4alkyl, C 3-C 6cycloalkyl, C 1-C 4alkoxyl group, C 3-C 4thiazolinyl, C 1-C 4alkoxy-C 1-C 4alkyl, represents optionally by fluorine, chlorine, bromine, trifluoromethyl, the monobasic phenyl of methyl or methoxy, represents optionally by the monobasic benzyl of fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxyl group,
R 7most preferably represent methylidene, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or allyl group,
R 6and R 7most preferably represent that wherein an optional methylene radical is by the C of oxygen or sulphur replacement 4-C 5alkylidene group.
W the most particularly preferably represents hydrogen or methyl,
X the most particularly preferably represents chlorine or methyl,
Y the most particularly preferably represents hydrogen or methyl,
Z the most particularly preferably represents one of following radicals
V 1the most particularly preferably represent fluorine, chlorine, methyl, sec.-propyl, methoxyl group, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2the most particularly preferably represent hydrogen, fluorine, chlorine or trifluoromethyl,
A is represent methylidene or ethyl the most particularly preferably,
D is represent methylidene or ethyl the most particularly preferably,
The A C that the most particularly preferably representative optionally replaces together with D 4-C 5alkane two bases, in described alkane two bases, an optional methylene radical is replaced by oxygen, and described alkane two bases are optionally by another C 1-C 2alkane two bases replace, or representative is optionally by fluorine, methyl or trifluoromethyl one or dibasic C 3alkane two bases,
G the most particularly preferably represents hydrogen (a) or represents one of following radicals
-SO 2-R 3 (d)，
Wherein
L represents oxygen, and
M represents oxygen,
R 1the most particularly preferably represent C 1-C 6alkyl or cyclopropyl,
R 2the most particularly preferably represent C 1-C 8alkyl or C 1-C 4alkoxy-C 2-C 3alkyl,
R 3the most particularly preferably represent methylidene, ethyl or sec.-propyl.
Above-mentioned general or preferred group definition or set forth combination with one another as required, comprises the combination between scope and preferable range separately.It had both been applicable to final product, and was therefore also applicable to precursor and intermediate.
The preferred formula of the present invention (I) compound, the combination that comprises above-mentioned preferred meaning.
The preferred formula of the present invention (I) compound, the combination that comprises above-mentioned more preferably implication.
The most preferred formula of the present invention (I) compound, the combination that comprises above-mentioned most preferably implication.
The most particularly preferred formula of the present invention (I) compound, the combination that comprises above-mentioned the most particularly preferably implication.
Saturated or unsaturated alkyl, alkyl or alkenyl for example, or even with heteroatomic combination, alkoxyl group for example, can be respectively all straight chain or with side chain.
Except as otherwise noted, otherwise the optional group replacing can be all monosubstituted or polysubstituted, and wherein, in polysubstituted situation, substituting group can be identical or different.
The compound of mentioning in Preparation Example, also can propose especially with following formula (I-1-a) compound:
table 1:
W X Y V 1 V 2
H CH 3 H 4-Cl H
H CH 3 CH 3 4-Cl H
CH 3 CH 3 CH 3 4-Cl H
H CH 3 H 3-Cl H
H CH 3 CH 3 3-Cl H
CH 3 CH 3 CH 3 3-Cl H
H CH 3 H 2-Cl 4-Cl
H CH 3 CH 3 2-Cl 4-Cl
CH 3 CH 3 CH 3 2-Cl 4-Cl
H CH 3 H 4-CF 3 H
H CH 3 CH 3 4-CF 3 H
CH 3 CH 3 CH 3 4-CF 3 H
H CH 3 H 4-F H
H CH 3 CH 3 4-F H
CH 3 CH 3 CH 3 4-F H
H CH 3 H 4-CH 3 H
H CH 3 CH 3 4-CH 3 H
W X Y V 1 V 2
CH 3 CH 3 CH 3 4-CH 3 H
H Cl H 4-Cl H
H Cl H 3-Cl H
H Cl H 4-CF 3 H
H Cl H - 4-F H
H Cl H 2-Cl 4-Cl
table 2:
W X Y V 1 V 2
H CH 3 H 4-Cl H
H CH 3 CH 3 4-Cl H
CH 3 CH 3 CH 3 4-Cl H
H CH 3 H 3-Cl H
H CH 3 CH 3 3-Cl H
CH 3 CH 3 CH 3 3-Cl H
H CH 3 H 2-Cl 4-Cl
H CH 3 CH 3 2-Cl 4-Cl
CH 3 CH 3 CH 3 2-Cl 4-Cl
H CH 3 H 4-CF 3 H
H CH 3 CH 3 4-CF 3 H
CH 3 CH 3 CH 3 4-CF 3 H
H CH 3 H 4-F H
H CH 3 CH 3 4-F H
CH 3 CH 3 CH 3 4-F H
H CH 3 H 4-CH 3 H
H CH 3 CH 3 4-CH 3 H
W X Y V 1 V 2
CH 3 CH 3 CH 3 4-CH 3 H
H Cl H 4-Cl H
H Cl H 4-Cl H
H Cl H 4-CF 3 H
H Cl H 4-F H
H Cl H 2-Cl 4-Cl
(II a), the preferred meaning of (II b), (II c), above listed group that (II d) and (II e) compound (" herbicide-safener ") is relevant is defined as follows to the formula of improving farm crop tolerance.
N preferably represents numeral 0,1,2,3 or 4.
A 1preferably represent one of divalent heterocyclic group shown below
A 2methylene radical or ethylidene that preferably representative is optionally replaced by methyl, ethyl, methoxycarbonyl or ethoxycarbonyl separately.
R 21preferred representation hydroxy, sulfydryl, amino, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert.-butoxy, methylthio group, ethylmercapto group, positive rosickyite base or isopropyl sulfenyl, positive butylthio, isobutyl sulfenyl, secondary butylthio or tertiary butylthio, methylamino, ethylamino, n-propyl amino or isopropylamino, normal-butyl amino, isobutylamino, sec-butyl amino or tertiary butyl amino, dimethylamino or diethylamino.
R 22preferred representation hydroxy, sulfydryl, amino, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert.-butoxy, methylthio group, ethylmercapto group, positive rosickyite base or isopropyl sulfenyl, positive butylthio, isobutyl sulfenyl, secondary butylthio or tertiary butylthio, methylamino, ethylamino, n-propyl amino or isopropylamino, normal-butyl amino, isobutylamino, sec-butyl amino or tertiary butyl amino, dimethylamino or diethylamino.
R 23methyl, ethyl, n-propyl or sec.-propyl that preferably representative is optionally replaced by fluorine, chlorine and/or bromine separately.
R 24preferably represent hydrogen, separately optionally by the methyl of fluorine and/or chlorine replacement, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, propenyl, butenyl, proyl or butynyl, methoxymethyl, ethoxyl methyl, methoxy ethyl, ethoxyethyl group, dioxolane ylmethyl, furyl, furyl methyl, thienyl, thiazolyl, piperidyl, or optionally by fluorine, chlorine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, the phenyl that sec-butyl or the tertiary butyl replace.
R 25preferably represent hydrogen, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, propenyl, butenyl, proyl or the butynyl that optionally by fluorine and/or chlorine, are replaced separately, methoxymethyl, ethoxyl methyl, methoxy ethyl, ethoxyethyl group, dioxolane ylmethyl, furyl, furyl methyl, thienyl, thiazolyl, piperidyl or the phenyl optionally being replaced by fluorine, chlorine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, or and R 24group-CH that representative is optionally replaced or replaced by two substituting groups by methyl, ethyl, furyl, phenyl, fused benzene rings together 2-O-CH 2-CH 2-and-CH 2-CH 2-O-CH 2-CH 2one of-, described two substituting groups form 5 or 6 yuan of carbocyclic rings together with the C atom being connected with them.
R 26preferably represent hydrogen, cyano group, fluorine, chlorine, bromine, or representative is separately optionally by methyl, ethyl, n-propyl or sec.-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the phenyl of fluorine, chlorine and/or bromine replacement.
R 27preferably represent hydrogen, methyl, ethyl, n-propyl or the sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl that optionally by hydroxyl, cyano group, fluorine, chlorine, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, are replaced.
R 28preferably represent hydrogen, cyano group, fluorine, chlorine, bromine, or representative is separately optionally by methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the phenyl of fluorine, chlorine and/or bromine replacement.
X 1preferably represent nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chloro difluoromethyl, fluoro dichloromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, difluoro-methoxy or trifluoromethoxy.
X 2preferably represent hydrogen, nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chloro difluoromethyl, fluoro dichloromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, difluoro-methoxy or trifluoromethoxy.
X 3preferably represent hydrogen, nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chloro difluoromethyl, fluoro dichloromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, difluoro-methoxy or trifluoromethoxy.
R 29preferably represent hydrogen, methyl, ethyl, n-propyl or sec.-propyl.
R 30preferably represent hydrogen, methyl, ethyl, n-propyl or sec.-propyl.
R 31preferably represent hydrogen, separately optionally by cyano group, fluorine, chlorine, methoxyl group, oxyethyl group, the methyl that positive propoxy or isopropoxy replace, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert.-butoxy, methylthio group, ethylmercapto group, positive rosickyite base or isopropyl sulfenyl, positive butylthio, isobutyl sulfenyl, secondary butylthio or tertiary butylthio, methylamino, ethylamino, n-propyl amino or isopropylamino, normal-butyl is amino, isobutylamino, sec-butyl amino or the tertiary butyl are amino, dimethylamino or diethylamino, or separately optionally by cyano group, fluorine, chlorine, bromine, methyl, ethyl, the cyclopropyl that n-propyl or sec.-propyl replace, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyl oxygen base, cyclobutyl oxygen base, cyclopentyloxy, cyclohexyl oxygen base, cyclopropyl sulfenyl, cyclobutyl sulfenyl, cyclopentyl sulfenyl, cyclohexyl sulfenyl, cyclopropylamino, cyclobutyl is amino, cyclopentyl amino or cyclohexyl are amino.
R 32preferably represent hydrogen, methyl, ethyl, n-propyl or the sec.-propyl, normal-butyl, isobutyl-or the sec-butyl that optionally by cyano group, hydroxyl, fluorine, chlorine, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, are replaced separately, the propenyl, butenyl, proyl or the butynyl that optionally by cyano group, fluorine, chlorine or bromine, are replaced separately or the cyclopropyl, cyclobutyl, cyclopentyl or the cyclohexyl that optionally by cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, are replaced separately.
R 33preferably represent hydrogen, separately optionally by cyano group, hydroxyl, fluorine, chlorine, methoxyl group, oxyethyl group, the methyl that positive propoxy or isopropoxy replace, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-or sec-butyl, separately optionally by cyano group, fluorine, the propenyl that chlorine or bromine replaces, butenyl, proyl or butynyl, separately optionally by cyano group, fluorine, chlorine, bromine, methyl, ethyl, the cyclopropyl that n-propyl or sec.-propyl replace, cyclobutyl, cyclopentyl or cyclohexyl, or optionally by nitro, cyano group, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, trifluoromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, the phenyl that difluoro-methoxy or trifluoromethoxy replace, or with R 32representative is separately optionally by fourth-Isosorbide-5-Nitrae-bis-base (trimethylene), penta-1 of methyl or ethyl replacement, 5-bis-bases, 1-oxa-fourth-Isosorbide-5-Nitrae-bis-base or 3-oxa-penta-1,5-bis-bases together.
X 4preferably represent nitro, cyano group, carboxyl, formamyl, formyl radical, sulfamyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, trifluoromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, difluoro-methoxy or trifluoromethoxy.
X 5preferably represent nitro, cyano group, carboxyl, formamyl, formyl radical, sulfamyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl, trifluoromethyl, methoxyl group, oxyethyl group, positive propoxy or isopropoxy, difluoro-methoxy or trifluoromethoxy.
More preferably as the formula of herbicide-safener, (the II a) example of compound is listed in the table below in 3 in the present invention.
table 3:(II is examples of compounds a) for formula
The present invention is more preferably listed in the table below in 4 as the example of formula (II b) compound of herbicide-safener.
table 4:formula (II b) examples of compounds
The present invention is more preferably listed in the table below in 5 as the example of formula (IIc) compound of herbicide-safener.
table 5:formula (II c) examples of compounds
The present invention is more preferably listed in the table below in 6 as the example of formula (II d) compound of herbicide-safener.
table 6:formula (II d) examples of compounds
The present invention is more preferably listed in the table below in 7 as the example of formula (II e) compound of herbicide-safener.
table 7:formula (II e) examples of compounds
Most preferably as the compound [component (b ')] that improves farm crop tolerance, have: cloquitocet_mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyrdiethyl, Xie Cao oxazole, fenclorim, cumyluron, daimuron, dimepiperate and Compound I I e-5 and II e-11, lay special stress on cloquitocet_mexyl and mefenpyrdiethyl.
The present invention treats that (II a) compound is known compound, and/or can be by known method preparation (referring to WO-A-91/07874, WO-A-95/07897) itself as the general formula of safener.
The present invention treats that general formula (II b) compound as safener is known compound, and/or can be by known method preparation (referring to EP-A-191736) itself.
The present invention treats that general formula (II c) compound as safener is known compound, and/or can be by known method preparation (referring to DE-A-2218097, DE-A-2350547) itself.
The present invention treats that general formula (II d) compound as safener is known compound, and/or can be by known method preparation (referring to DE-A-19621522/US-A-6235680) itself.
The present invention treats that general formula (II e) compound as safener is known compound, and/or can be by known method preparation (referring to WO-A-99/66795/US-A-6251827) itself.
The example that comprises respectively the selective herbicidal binding substances of the present invention of one of a kind of formula (I) active compound and above-mentioned safener is listed in the table below in 8.
table 8:binding substances example of the present invention
Formula (I) active compound Safener
I-a Cloquitocet_mexyl
Formula (I) active compound Safener
I-a fenchlorazole-ethyl
I-a isoxadifen-ethyl
I-a Mefenpyrdiethyl
I-a Xie Cao oxazole
I-a Fenclorim
I-a Cumyluron
I-a Daimuron
I-a Dimepiperate
I-a II e-11
I-a II e-5
I-b Cloquitocet_mexyl
I-b fenchlorazole-ethyl
I-b isoxadifen-ethyl
I-b Mefenpyrdiethyl
I-b Xie Cao oxazole
I-b Fenclorim
I-b Cumyluron
I-b Daimuron
I-b Dimepiperate
I-b II e-11
I-b II e-5
I-c Cloquitocet_mexyl
I-c fenchlorazole-ethyl
I-c isoxadifen-ethyl
I-c Mefenpyrdiethyl
I-c Xie Cao oxazole
I-c Fenclorim
I-c Cumyluron
I-c Daimuron
I-c Dimepiperate
Formula (I) active compound Safener
I-c II e-11
I-c II e-5
I-d Cloquitocet_mexyl
I-d fenchlorazole-ethyl
I-d isoxadifen-ethyl
I-d Mefenpyrdiethyl
I-d Xie Cao oxazole
I-d Fenclorim
I-d Cumyluron
I-d Daimuron
I-d Dimepiperate
I-d IIe-11
I-d II e-5
I-e Cloquitocet_mexyl
I-e fenchlorazole-ethyl
I-e isoxadifen-ethyl
I-e Mefenpyrdiethyl
I-e Xie Cao oxazole
I-e Fenclorim
I-e Cumyluron
I-e Daimuron
I-e Dimepiperate
I-e II e-11
I-e II e-5
I-f Cloquitocet_mexyl
I-f fenchlorazole-ethyl
I-f isoxadifen-ethyl
I-f Mefenpyrdiethyl
I-f Xie Cao oxazole
I-f Fenclorim
Formula (I) active compound Safener
I-f Cumyluron
I-f Daimuron
I-f Dimepiperate
I-f II e-11
I-f II e-5
I-g Cloquitocet_mexyl
I-g fenchlorazole-ethyl
I-g isoxadifen-ethyl
I-g Mefenpyrdiethyl
I-g Xie Cao oxazole
I-g Fenclorim
I-g Cumyluron
I-g Daimuron
I-g Dimepiperate
I-g II e-11
I-g II e-5
Surprisingly, have now found that substituted pyrazolidin-3 of the 4-xenyl of general formula defined above (I), 5-derovatives and the above active agent combinations of safener (toxinicide) of listed (b ') part, when thering is extraordinary useful plants tolerance, also there is extra high weeding activity, can be for selectivity controlling weeds in various crop, described crop is cereal (especially wheat) particularly, and soybean, potato, corn and paddy rice.
In the present invention, will be understood that surprisingly, from numerous known can be to antiweed to the safener or toxinicide of the destructive drug effect of farm crop, particularly above the compound of listed (b ') part is applicable to almost entirely compensate pyrazolidine-3 that 4-xenyl replaces, the destructive drug effect of 5-derovatives to farm crop, and can to removing the weeding activity of weeds, not have a negative impact with any significant degree.
In the present invention, can be emphasized be in (b ') part more preferably with the particularly advantageous drug effect of most preferred combination material standed for, particularly not can to cereal plant, farm crop such as wheat, barley and rye and corn and paddy rice cause disadvantageous effect aspect.
For example, according to method (A-α), take (chloroformyl)-3-[(6-methyl-3-(4-methyl) phenyl) phenyl] ketenes and hexahydro-pyridazine be raw material, the process of the inventive method can represent by following reaction scheme:
For example, according to method (A-β), take 3-[(6-methyl-3-(3-chloro-phenyl-)] phenyl ethyl malonate and hexahydro-pyridazine be raw material, the process of the inventive method can represent by following reaction scheme:
For example, according to method (A γ), take 1-ethoxy carbonyl-2-[6-methyl-3-(4-chloro-phenyl-) phenyl acetyl] hexahydro-pyridazine is raw material, reaction process can represent by following route:
According to method (B), with the bromo-6-aminomethyl phenyl of 8-[3-]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and 4-chlorophenylboronic acid are raw material, reaction process can represent by following route:
According to method (C α), with the chloro-5-of 8-[(2-(3-chloro-phenyl-) phenyl)]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and pivalyl chloride are raw material, the process of the inventive method can represent by following reaction scheme:
According to method (C) (change programme β), with 8-[(6-methyl-3-(4-p-methoxy-phenyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and diacetyl oxide are raw material, the process of the inventive method can represent by following reaction scheme:
According to method (D), with 8-[(2,6-dimethyl-3-(4-chloro-phenyl-)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and carbonochloridic acid ethoxy ethyl ester are raw material, the process of the inventive method can represent by following reaction scheme:
According to method (E), with the chloro-5-of 8-[(2-(4-fluorophenyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and chloro list bamic acid methyl esters are raw material, the process of the inventive method can represent by following reaction scheme:
According to method (F), with 8-[(2,4,6-trimethylammonium-3-(4-aminomethyl phenyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and Methanesulfonyl chloride are raw material, reaction process can represent by following reaction scheme:
According to method (G), with 8-[(6-trimethylammonium-3-(4-chloro-phenyl-)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and methyl thio-phosphoryl chlorine 2,2,2-trifluoroethyl ester is raw material, reaction process can represent by following reaction scheme:
According to method (H), with the chloro-5-of 8-[(2-(4-trifluoromethyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and NaOH are component, the process of the inventive method can represent by following reaction scheme:
According to method (I) (change programme α), with 8-[(6-methyl-3-(3-trifluoromethyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and ethyl isocyanate are raw material, reaction process can represent by following reaction scheme:
According to method (I) (change programme β), with the chloro-5-of 8-[(2-(4-fluorophenyl)) phenyl]-1,6-diazabicyclo [4.3.0 1.6] nonane-7,9-diketone and dimethylcarbamyl chloride are raw material, reaction process can represent by following reaction scheme:
As aforesaid method (A) (α) the halo carbonyl ketenes of the formula of raw material (II) be new compound.They can by the preparation of method known in principle (for example, referring to, Org.Prep.Proced.Int., (4), 155-158,1975 and DE 1 945 703).Thus, for example, formula (II) compound is made by following reaction:
Wherein
W, X, Y and Z define as above, and
Hal represents chlorine or bromine
If be suitably under the existence of catalyzer, for example, under the existence of dimethyl formamide, methyl stearyl (steryl) methane amide or triphenyl phosphine, if and be suitably under the existence of alkali, for example, under the existence of pyridine or triethylamine, the substituted-phenyl propanedioic acid of formula (X VII) reacts with carboxylic acid halides, for example react with thionyl chloride, phosphorus chloride (V), phosphorus chloride (III), oxalyl chloride, carbonyl chloride or thionyl bromide
Wherein
W, X, Y and Z definition are as above.
The substituted-phenyl propanedioic acid of formula (X VII) is new compound.They can by currently known methods with simple mode prepare (referring to, Organikum for example, VEB Deutscher Verlag der Wissenschaften, 1977, the 517 pages of Berlin, EP-A-528 156, WO 97/36868, WO 97/01535 and WO 98/05638).
Thus, the phenylmalonic acid of formula (X VII) is made by following reaction:
Wherein
W, X, Y and Z definition are as above
The phenylmalonic acid ester of formula (III) is first hydrolyzed under the existence of alkali and solvent, then careful acidifying (EP-528 156, WO 97/36868, WO 97/01535)
Wherein
W, X, Y and Z define as above,
And
U represents C 1-C 8alkoxyl group.
The malonic ester of formula (III) is new compound
Wherein
W, X, Y and Z definition are as above
And
U represents C 1-C 8alkoxyl group.
They can be by the preparation of substantially known organic chemistry method (for example, referring to, Tetrahedron Lett. 27, 2763 (1986) and Organikum, VEB Deutscher der Wissenschaften, rise 1977, the 587 pages of Berlin), also can be used as the raw material of the inventive method A (β).
Some hydrazines as the formula (IV) of the inventive method A (α) and A (β) raw material are known compounds
A-NH-NH-D (IV)，
Wherein
A and D define as above,
And/or they can be by known in the literature method preparation (for example, referring to, Liebigs Ann.Chem. 585, 6 (1954); Reaktionen der organischen Synthese, C.Ferri, the 212nd, 513 pages; Georg Thieme Verlag Stuttgart, 1978; Liebigs Ann.Chem. 443, 242 (1925); Chem.Ber. 98, 2551 (1965), EP-A 508 126, and WO 92/16510, and WO 99/47525, WO 01/17972).
Required formula (V) compound of the inventive method A (γ) is new compound
Wherein
A, D, W, X, Y, Z and R 8definition as above.
The acylhydrazine carbamate (carbazate) of formula (V) makes by for example following reaction:
The substituted-phenyl acetogenin acidylate (Chem.Reviews of the formula for carbazates (X IX) of formula (X VIII) 52, 237-416 (1953); Bhattacharya, Indian J.Chem. 6, 341-5,1968)
Wherein
A, R 8define as above with D,
Wherein
W, X, Y and Z define as above,
The leavings group that T representative is introduced by activating carboxy acid's reagent place, described reagent is carbonyl dimidazoles for example, carbonyl diurethane imide (for example dicyclohexyl carbodiimide (dicyclohexylcarbodiimide)), phosphorus esterification reagent (POCl for example 3, BOP-Cl), halogenating agent, for example thionyl chloride, oxalyl chloride, carbonyl chloride, SULPHURYL CHLORIDE (for example toluene sulfonyl chloride) or chloro-formic ester.
The carbazates of some formulas (X VIII) is known compound, or they can be prepared by substantially known organic chemistry method.
Some formulas (X IX) compound is new compound, or they can prepare by substantially known method, for example WO 99,/43 649, WO 99,/48 869, WO 99,/55 673.
The biphenyl acetic acid of the formula (X X) that preparation formula (X IX) compound is required makes by for example following reaction,
Wherein
W, X and Y define as above:
The biphenyl acetic acid ester of formula (X XI) under the existence of acid or alkali, under the existence of solvent, be hydrolyzed under substantially known standard state
Wherein
W, X, Y and R 8definition as above.
Some formulas (X X) and formula (X XI) compound are new compounds, can prepare by being similar to the method described in WO 99/48869.
Formula (X XI) compound makes by routine method as be shown in the examples (Q), and the method is as described below,
Wherein
W, X, Y, Z and R 8define as above:
The phenylacetic acid ester of formula (X XI-a) is under the existence of the phenyl-boron dihydroxide of formula (VI), under the existence of alkali, if and be suitably in catalyzer (preferably palladium salt or palladium complex, for example four (triphenylphosphines) close palladium (0)) existence under react, the Z definition of its Chinese style (VI) as above
Wherein
R 8, W, X and Y definition as above, and
Z ' represents halogen (particularly bromine).
The phenylacetic acid ester of some formulas (X XI-a) is known in applying for WO 97,/01 535, WO 97,/36 868, WO 98,/05 638, or they can be prepared by the method in described application.
Some formulas as aforesaid method (B) raw material (I '-a) to (I '-g) compound be known compound (WO 97,/01 535, WO 97,/36 868, WO 98,/05 638, WO 96,/35 664, WO 97,/02 243 and WO 98,/05 638), its Chinese style (I '-a) A, D, W, X and the Y to (I '-g) defines as above, and Z ' represents chlorine or bromine, preferred bromine; Or they can be by the method preparation in described application.
The boric acid of some formulas (VI) is commercial compound, or they can be prepared with plain mode by substantially known method
Wherein
Z definition as above.
As the inventive method (C), (D), (E), (F), (G), (H) and (I) carboxylic acid halides of the formula of raw material (VII), the acid anhydrides of formula (VIII), the chloro-formic ester of formula (IX) or chloroformic acid thioesters, the chloro list thiocarboxylic of formula (X) or chloro dithio formate, the SULPHURYL CHLORIDE of formula (XI), the P contained compound of formula (XII), the corresponding metal hydroxides of formula (X III) and (X IV), metal alkoxides or amine, and the urea chloride of the isocyanic ester of formula (X V) and formula (X VI) is substantially known organic or inorganic chemical compound.
The inventive method (A-α) is characterised in that, the hydrazine of formula (IV) or its salt under the existence of thinner, and if be suitably under the existence of acid acceptor, react with the ketenes carboxylic acid halides of formula (II).
The thinner that is suitable for using in the inventive method (A-α) is all inert organic solvents.Preferably use the hydrocarbon of optional chloro, for example 1,3,5-Three methyl Benzene, chlorobenzene and dichloro benzene,toluene,xylene, also has ether, for example dibutyl ether, glycol dimethyl ether, diglyme and phenyl ether, also have polar solvent, for example dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide or N-Methyl pyrrolidone.
The acid acceptor that the applicable acid acceptor of making change programme of the present invention (A-α) is all routines.
Preferably use tertiary amine, for example triethylamine, pyridine, diazabicyclo octane (DABCO), diazabicyclo undecane (DBU), diazabicyclo-nonene (DBN), H ü nig alkali and DMA.
While implementing change programme of the present invention (A-α), temperature of reaction can change in relatively wide scope.Advantageously, method 0 ℃ to 250 ℃, preferably at the temperature of 50 ℃ to 220 ℃, implement.
Method of the present invention (A-α) is advantageously under atmospheric pressure implemented.
While implementing method of the present invention (A-α), formula (III) and formula (IV) reactive component, if and suitable acid acceptor, conventionally with approximately equimolar amount, use, A, the D of its Chinese style (III) and formula (IV), W, X, Y and Z define as above, and Hal represents halogen.Yet, also can use a kind of or other components of excessive (being up to 5mol) relatively in a large number.
Method (A-β) is characterised in that, the hydrazine of formula (IV) or its salt under the existence of alkali with malonic ester or the Malonamide condensation of formula (II), as above, U, the W of formula (III), X, Y and Z definition are as above for the A of its Chinese style (IV) and D definition.
The thinner that is suitable for using in the inventive method (A-β) is all inert organic solvents.Preferably use the hydrocarbon of optional halo, for example toluene, dimethylbenzene, 1,3,5-Three methyl Benzene, chlorobenzene and dichlorobenzene, also have ether, for example dibutyl ether, tetrahydrofuran (THF), diox, phenyl ether, glycol dimethyl ether and diglyme, also has polar solvent, for example dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone, and alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol.
The alkali (deprotonation agent) that is applicable to implement the inventive method (A-β) is all conventional proton acceptors.Preferably use alkali and alkaline earth metal ions oxide compound, oxyhydroxide and carbonate, for example sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood and calcium carbonate, above-claimed cpd also can be used under the existence of phase-transfer catalyst, and described catalyzer is triethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, Adogen 464 (=methyl three (C for example 8-C 10ammonium chloride) or TDA 1 (=tri-(methoxyethoxyethyl) amine) alkyl).Also can use basic metal, for example sodium or potassium.Same alkali and alkaline earth metal ions amide and the hydride being in addition applicable to, for example ammonification sodium, sodium hydride and hydrolith, also have alkoxy base metal, for example sodium methylate, sodium ethylate and potassium tert.-butoxide.
Also can use tertiary amine, for example triethylamine, pyridine, diazabicyclo octane (DABCO), diazabicyclo undecane (DBU), diazabicyclo-nonene (DBN), H ü nig alkali and DMA.
While implementing method of the present invention (A-β), temperature of reaction can change in relatively wide scope.Generally speaking, reaction 0 ℃ to 280 ℃, preferably at the temperature of 50 ℃ to 180 ℃, carry out.
Method of the present invention (A-β) is under atmospheric pressure implemented conventionally.
While implementing method of the present invention (A-β), formula (III) and formula (IV) reactive component are used with approximately equimolar amount conventionally.Yet, also can use a kind of or other components of excessive (being up to 3mol) relatively in a large number.
Method (A-γ) is characterised in that, formula (V) compound issues raw intramolecular condensation in the existence of alkali, A, D, W, X, Y, Z and the R of its Chinese style (V) 8definition as above.
The thinner that is suitable for using in the inventive method (A-γ) is all inert organic solvents.Preferably use hydrocarbon, for example toluene and dimethylbenzene, also has ether, for example dibutyl ether, tetrahydrofuran (THF), diox, glycol dimethyl ether and diglyme, also has polar solvent, for example dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide and N-Methyl pyrrolidone, and alcohol, for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol and the trimethyl carbinol.
The alkali (deprotonation agent) that is applicable to implement the inventive method (A-γ) is all conventional proton acceptors.Preferably use alkali and alkaline earth metal ions oxide compound, oxyhydroxide and carbonate, for example sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, salt of wormwood and calcium carbonate, above-claimed cpd also can be used under the existence of phase-transfer catalyst, and described catalyzer is triethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, Adogen 464 (=methyl three (C for example 8-C 10ammonium chloride) or TDA 1 (=tri-(methoxyethoxyethyl) amine) alkyl).Also can use basic metal, for example sodium or potassium.Same alkali and alkaline earth metal ions amide and the hydride being in addition applicable to, for example ammonification sodium, sodium hydride and hydrolith, also have alkoxy base metal, for example sodium methylate, sodium ethylate and potassium tert.-butoxide.
While implementing method of the present invention (A-γ), temperature of reaction can change in relatively wide scope.Generally speaking, reaction 0 ℃ to 250 ℃, preferably at the temperature of 50 ℃ to 150 ℃, carry out.
Method of the present invention (A-γ) is under atmospheric pressure implemented conventionally.
While implementing method of the present invention (A-γ), formula (V) reactive component and deprotonation choline are used with the equimolar amount of about twice conventionally.Yet, also can use a kind of or other components of excessive (being up to 3mol) relatively in a large number.
The catalyzer that is applicable to implement the inventive method (B) is palladium (0) title complex.Preference closes palladium as four (triphenylphosphines).If suitable, also can use palladium (II) compound, for example PdCl 2.
The acid acceptor that is applicable to implement the inventive method (B) is inorganic or organic bases.Preferably include alkaline-earth metal or alkali metal hydroxide, acetate, carbonate or supercarbonate, sodium hydroxide for example, potassium hydroxide, hydrated barta or ammonium hydroxide, sodium acetate, potassium acetate, lime acetate or ammonium acetate, sodium carbonate, salt of wormwood, cesium carbonate or volatile salt, sodium bicarbonate or saleratus, alkaline metal fluoride cpd, cesium fluoride for example, and tertiary amine, Trimethylamine 99 for example, triethylamine, Tributylamine, N, accelerine, N, N-dimethyl benzylamine, pyridine, N-methyl piperidine, N-methylmorpholine, N, N-dimethyl aminopyridine, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN) or diazabicyclo undecane (DBU).
The thinner that is applicable to implement the inventive method (B) is water, organic solvent or its any mixture.The example that can mention has: aliphatic hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbons, for example sherwood oil, hexane, heptane, hexanaphthene, methylcyclohexane, benzene,toluene,xylene or naphthane; Halohydrocarbon, for example chlorobenzene, dichlorobenzene, methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride, trichloroethane or zellon; Ether, for example ether, diisopropyl ether, methyl tertiary butyl ether, tert amyl methyl ether(TAME), diox, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, 1,2-diethoxyethane, diethylene glycol dimethyl ether or methyl-phenoxide; Alcohol, for example methyl alcohol, ethanol, n-propyl alcohol or Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol or the trimethyl carbinol, ethylene glycol, the third-1,2-glycol, ethoxy ethanol, methyl cellosolve, diglycol monotertiary methyl ether, diglycol monotertiary methyl ether; Water.
The temperature of reaction of the inventive method (B) can change in relatively wide scope.Generally speaking, reaction 0 ℃ to+140 ℃, preferably at the temperature of 50 ℃ to+100 ℃, carry out.
While implementing method of the present invention (B), the boric acid of formula (VI) and formula (I '-a) to formula (I '-g) compound with 1: 1 to 3: 1, preferably the mol ratio of 1: 1 to 2: 1 is used, the Z definition of its Chinese style (VI) as above, formula (I '-a) to A, D, W, X, Y and the Z ' definition of formula (I '-g) as above.Generally speaking, the formula of every mole (I '-a) to formula (I '-g) compound use 0.005 to 0.5mol, the preferred catalyzer of 0.01mol to 0.1mol.The common excessive use of alkali.
Method (E-α) is characterised in that, if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, (I a) compound reacts with the carboxylic acid halides of formula (VII) respectively formula.
The thinner that is suitable for using in the inventive method (C-α) is all solvents to carboxylic acid halides inertia.Preferably use hydrocarbon, for example gasoline, benzene,toluene,xylene and 1,2,3,4-tetraline, also has halohydrocarbon, for example methylene dichloride, chloroform, tetracol phenixin, chlorobenzene and orthodichlorobenzene, also have ketone, for example acetone and methyl isopropyl Ketone, also has ether, for example ether, tetrahydrofuran (THF) He diox, also have carboxylicesters, for example ethyl acetate, and intensive polar solvent, for example dimethyl sulfoxide (DMSO) and tetramethylene sulfone.In the situation that the stability to hydrolysis of carboxylic acid halides allows, reaction also can be carried out under the existence of water.
The acid binding agent that is suitable for the inventive method (C-α) reaction is all conventional acid receptors.Preferably use tertiary amine, for example triethylamine, pyridine, diazabicyclo octane (DABCO), diazabicyclo undecane (DBU), diazabicyclo-nonene (DBN), H ü nig alkali and N, accelerine, also has alkaline earth metal oxide, for example magnesium oxide and calcium oxide, also have alkali and alkaline earth metal ions carbonate, for example sodium carbonate, salt of wormwood and calcium carbonate, and alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide.
The temperature of reaction of the inventive method (C-α) can change in relatively wide scope.Generally speaking, reaction-20 ℃ to+150 ℃, preferably at the temperature of 0 ℃ to 100 ℃, carry out.
While implementing method of the present invention (C-α), the carboxylic acid halides of formula (I-a) raw material and formula (VII) is used with about equivalent conventionally separately.Yet, also can use the carboxylic acid halides of excessive (being up to 5mol) relatively in a large number.Aftertreatment is undertaken by ordinary method.
Method (C-β) is characterised in that, if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, (I is the anhydride reaction of compound and formula (VIII) a) for formula.
The thinner that is suitable for using in the inventive method (C-β) is preferably the preferred diluent while using carboxylic acid halides.In addition, excessive acid anhydrides also can be used as thinner simultaneously.
If suitable, add the acid binding agent in method (C-β) to be preferably the preferred acid bonding agent while using carboxylic acid halides.
The temperature of reaction of the inventive method (C-β) can change in relatively wide scope.Generally speaking, reaction-20 ℃ to+150 ℃, preferably at the temperature of 0 ℃ to 100 ℃, carry out.
While implementing method of the present invention (C-β), (the I a) acid anhydrides of raw material and formula (VIII) is used with about equivalent formula conventionally separately.Yet, also can use the acid anhydrides of excessive (being up to 5mol) relatively in a large number.Aftertreatment is undertaken by ordinary method.
Generally speaking, the carboxylic acid of thinner and excessive acid anhydrides and generation is removed by distillation, or removes with organic solvent or water washing.
Method (D) is characterised in that, if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, (I a) compound reacts with chloro-formic ester or the chloroformic acid thioesters of formula (IX) respectively formula.
The acid binding agent that is applicable to the inventive method (D) reaction is all conventional acid receptors.Preferably use tertiary amine, for example triethylamine, pyridine, DABCO, DBU, DBA, H ü nig alkali and N, accelerine, also has alkaline earth metal oxide, for example magnesium oxide and calcium oxide, also have alkali and alkaline earth metal ions carbonate, for example sodium carbonate, salt of wormwood and calcium carbonate, and alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide.
The thinner that is applicable to the inventive method (D) is all solvents to chloro-formic ester or chloroformic acid thioesters inertia.Preferably use hydrocarbon, for example gasoline, benzene,toluene,xylene and 1,2,3,4-tetraline, also has halohydrocarbon, for example methylene dichloride, chloroform, tetracol phenixin, chlorobenzene and orthodichlorobenzene, also have ketone, for example acetone and methyl isopropyl Ketone, also has ether, for example ether, tetrahydrofuran (THF) He diox, also have carboxylicesters, for example ethyl acetate, and intensive polar solvent, for example dimethyl sulfoxide (DMSO) and tetramethylene sulfone.
While implementing method of the present invention (D), temperature of reaction can change in relatively wide scope.If reaction is carried out under the existence of thinner and acid binding agent, temperature of reaction is generally-20 ℃ to+100 ℃, preferably 0 ℃ to 50 ℃.
Method of the present invention (D) is under atmospheric pressure implemented conventionally.
While implementing method of the present invention (D), the chloro-formic ester of formula (I-a) raw material and suitable formula (IX) or chloroformic acid thioesters are used with about equivalent conventionally separately.Yet, also can use a kind of or other components of excessive (being up to 2mol) relatively in a large number.Aftertreatment is undertaken by ordinary method.Generally speaking, remove the salt being settled out, under decompression, remove thinner to concentrate remaining reaction mixture.
The inventive method (E) is characterised in that, formula (I-a) compound under the existence of thinner, and if be suitably under the existence of acid binding agent, react with formula (X) compound respectively.
In preparation method (E), 0 to 120 ℃, preferably at 20 to 60 ℃, the formula of every mole (I-a) raw material reacts with chloro list thiocarboxylic or the chloro dithio formate of the formula (X) of about 1mol.
If the applicable thinner adding suitable is all inertia polar organic solvents, for example ether, acid amides, sulfone, sulfoxide and haloalkane.
Preferably use dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dimethyl formamide or methylene dichloride.
In preferred embodiments, if by adding strong deprotonation agent, for example, add enol form (enolate) salt of sodium hydride or potassium tert.-butoxide preparation formula (I-a) compound, can exempt and add acid binding agent.
If use acid binding agent, described acid binding agent can be conventional inorganic or organic bases, for example sodium hydroxide, sodium carbonate, salt of wormwood, pyridine, triethylamine.
Reaction can under atmospheric pressure or under the condition of pressure rising be carried out, and preferably under atmospheric pressure carries out.Aftertreatment is undertaken by ordinary method.
The inventive method (F) is characterised in that, if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, formula (I-a) compound reacts with the SULPHURYL CHLORIDE of formula (XI) respectively.
In preparation method (F) ,-20 to 150 ℃, preferably at 20 to 70 ℃, the formula of every mole (I-a) raw material reacts with the SULPHURYL CHLORIDE of the formula (XI) of about 1mol.
If the applicable thinner adding suitable is all inertia polar organic solvents, for example ether, acid amides, nitrile, sulfone, sulfoxide or halohydrocarbon, for example methylene dichloride.
Preferably use dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dimethyl formamide, methylene dichloride.
In preferred embodiments, if for example, by adding the enolate of strong deprotonation agent (sodium hydride or potassium tert.-butoxide) preparation formula (I-a) compound, can exempt and add acid binding agent.
If use acid binding agent, described acid binding agent can be conventional inorganic or organic bases, for example sodium hydroxide, sodium carbonate, salt of wormwood, pyridine, triethylamine.
Reaction can under atmospheric pressure or under the condition of pressure rising be carried out, and preferably under atmospheric pressure carries out.Aftertreatment is undertaken by ordinary method.
Method (G) is characterised in that, if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, formula (I-a) compound reacts with the P contained compound of formula (XII) respectively.
In preparation method (G), for making formula (I-e) compound,-40 ℃ to 150 ℃, preferably-10 ℃ to 110 ℃ at, the formula of every mole (I a) compound and 1 to 2mol, preferably the P contained compound of 1 to 1.3mol formula (XII) reacts.
If the applicable thinner adding suitable is all inertia polar organic solvents, such as ether, acid amides, nitrile, alcohol, sulfide (sulphide), sulfone, sulfoxide etc.
Preferably use acetonitrile, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dimethyl formamide, methylene dichloride.
If the applicable acid binding agent adding suitable is conventional inorganic or organic bases, for example oxyhydroxide, carbonate or amine.The example that can mention has sodium hydroxide, sodium carbonate, salt of wormwood, pyridine, triethylamine.
Reaction can under atmospheric pressure or under the condition of pressure rising be carried out, and preferably under atmospheric pressure carries out.Aftertreatment is undertaken by conventional organic chemistry method.The final product making, preferably by crystallization, chromatogram purification or by " underpressure distillation ", is removed the method for volatile constituent and is carried out purifying under decompression.
Method (H) is characterised in that, if be suitably under the existence of thinner, formula (I-a) compound reacts with the metal hydroxides of formula (X III) or the amine of metal alkoxides or formula (X IV).
Be suitable in the inventive method (H) the preferred ether of thinner using, for example tetrahydrofuran (THF), diox, ether, or alcohol, for example methyl alcohol, ethanol, Virahol, and water.
Method of the present invention (H) is under atmospheric pressure implemented conventionally.
Temperature of reaction is generally-20 ℃ to 100 ℃, preferably 0 ℃ to 50 ℃.
The inventive method (I) is characterised in that, formula (I-a) compound reacts with following compound respectively:
(I-α) if be suitably under the existence of thinner, and if be suitably under the existence of catalyzer, react with formula (X V) compound; Or
(I-β) if be suitably under the existence of thinner, and if be suitably under the existence of acid binding agent, react with formula (X VI) compound.
In preparation method (I-α), 0 to 100 ℃, preferably at 20 to 50 ℃, the isocyanate reaction of the formula of the formula of every mole (I-a) raw material and about 1mol (X V).
If the applicable thinner adding suitable is all inert organic solvents, for example ether, acid amides, nitrile, sulfone, sulfoxide.
If suitable, can add catalyzer with accelerated reaction.Applicable make catalyzer be, advantageously organo-tin compound, for example dibutyl tin laurate (dibutyltin dilaurate).Reaction is preferably under atmospheric pressure carried out.
In preparation method (I-β) ,-20 to 150 ℃, preferably at 0 to 70 ℃, the formula of every mole (I-a) raw material reacts with the urea chloride of the formula (XVI) of about 1mol.
If the applicable thinner adding suitable is all inertia polar organic solvents, for example ether, acid amides, sulfone, sulfoxide or halohydrocarbon.
Preferably use dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dimethyl formamide or methylene dichloride.
In preferred embodiments, if for example, by adding the enolate of strong deprotonation agent (sodium hydride or potassium tert.-butoxide) preparation formula (I-a) compound, can exempt and add acid binding agent.
If use acid binding agent, described acid binding agent can be conventional inorganic or organic bases, for example sodium hydroxide, sodium carbonate, salt of wormwood, triethylamine or pyridine.
Reaction can under atmospheric pressure or under the condition of pressure rising be carried out, and preferably under atmospheric pressure carries out.Aftertreatment is undertaken by ordinary method.
Active compound has good plant tolerance, to the hypotoxicity of warm-blooded animal and good Environmental compatibility; Be suitable for protective plant and plant organ; improve the output of gathering; improve harvested material quality, and control animal pest, be particularly present in insect, arachnid and the nematode in agricultural, forest, gardening and leisure facilities, storage product and material protection and hygiene department.They are preferably used as crop protection agents.To common sensitivity and resistance species and all or some etap there is activity.Above-mentioned insect comprises:
Isopoda (Isopoda), for example, comb beach louse (Oniscus asellus), pillworm (Armadilliudium vulgare) and ball pillworm (Porcellio scaber).
Sufficient order (Diplopoda) doubly, for example, Blaniulus guttulatus.
Lip foot order (Chilopoda), for example, Geophilus carpophagust, Scutigera spp..
Comprehensive order (Symphyla), for example, Scutigerella immaculata.
Thysanura (Thysanura), for example, silverfish (Lepisma saccharina).
Collembola (Collembola), for example, arms Onychiurus arcticus (Onychiurus armatus).
Orthoptera (Orthoptera), for example, the Xi (Acheta domesticus) of family, Gryllotalpa spp (Gryllotalpa spp.), African migratory locust (Locusta migratoria migratorioides), black locust belong to (Melanoplus spp.), desert locust (Schistocerca gregaria).
Blattodea (Blattaria), for example, oriental cockroach (Blatta orientalis), periplaneta americana (Periplaneta americana), leucophaea maderae (Leucophaea maderae), blatta germanica (Blattella germanica).
Dermaptera (Dermaptera), for example, European earwig (Forficula auricularia).
Isoptera (Isoptera), for example, Reticulitermes (Reticulitermes spp.).
Anoplura (Phthiraptera), for example, body louse (Pediculus humanus corporis), Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), Trichodectes (Trichodectes spp.), Damalinia (Damalinia spp.).
Thysanoptera (Thysanoptera), for example, greenhouse bar hedge thrips (Hercinothrips femoralis), onion thrips (Thrips tabaci), palm thrips (Thrips palmi), alfalfa thrips (Frankliniella accidentalis).
Heteroptera (Heteroptera), for example, Eurygasterspp belongs to (Eurygaster spp.), Dysdercus intermedius, square butt stinkbug (Piesma quadrata), bed bug (Cimex lectularius), phodnius prolixus (Rhodnius prolixus), Triatoma (Triatoma spp.).
Homoptera (Homoptera), for example, wild cabbage aleyrodid (Aleurodes brassicae), cassava aleyrodid (Bemisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), cotten aphid (Aphis gossypii), brevicoryne brassicae (Brevicoryne brassicae), the hidden knurl aphid of tea Fischer (Cryptomyzus ribis), aphis fabae (Aphis fabae), apple aphid (Aphis pomi), eriosoma lanigerum (Eriosomal anigerum), mealy plum aphid (Hyalopterus arundinis), grape phylloxera (Phylloxera vastatrix), Pemphigus (Pemphigus spp.), grain aphid (Macrosiphum avenae), tumor aphid genus (Myzus spp.), phorodon aphid (Phorodon humuli), rhopalosiphum padi (Rhopalosiphum padi), Empoasca flavescens (Empoasca spp.), Euscelis bilobatus, rice green leafhopper (Nephotettix cincticeps), water wood hard a red-spotted lizard (Lecanium corni), black scale (Saissetia oleae), small brown rice planthopper (Laodelphax striatellus), brown paddy plant hopper (Nilaparvata lugens), red kidney Aspidiotus (Aonidiella aurantii), ivy Aspidiotus (Aspidiotus hederae), mealybug belongs to (Pseudococcus spp.), Psylla spp (Psylla spp.).
Lepidopteran (Lepidoptera), for example, Pectinophora gossypiella (Pectinophora gossypiella), loose looper (Bupalus piniarius), winter geometrid moth (Cheimatobia brumata), the thin moth of apple (Lithocolletis blancardella), apple ermine moth (Hyponomeuta padella), diamond-back moth (Plutella xylostella), malacosoma neustria (Malacosoma neustria), pornography and drug moth (Euproctis chrysorrhoea), Euproctis (Lymantria spp.), cotton lyonetid (Bucculatrix thurberiella), tangerine lyonetid (Phyllocnistis citrella), Agrotis (Agrotis spp.), cutworm belongs to (Euxoa spp.), the dirty Noctua (Feltia spp.) of cutting, earias insulana (Earias insulana), Heliothis (Heliothis spp.), lopper worm (Mamestra brassicae), small noctuid (Panolis flammea), Spodoptera (Spodoptera spp.), cabbage looper (Trichoplusia ni), codling moth (Carpocapsa pomonella), Pieris spp (Pieris spp.), straw borer spp (Chilo spp.), Pyrausta nubilalis (Hubern). (Pyrausta nubilalis), Anagasta kuehniella (Ephestia kuehniella), greater wax moth (Galleria mellonella), curtain rain moth (Tineola bisselliella), bag rain moth (Tinea pellionella), brownly knit moth (Hofmannophila pseudospretella), the yellow volume of flax moth (Cacoecia podana), Capua reticulana, spruce bunworm (Choristoneura fumiferana), grape codling moth (Clysia ambiguella) (Clysia ambiguella), tea long paper moth (Homona magnanima), the green volume moth of oak (Tortrix viridana), Cnaphaloceruss pp., Oulema oryzae (Oulema oryzae).
Coleoptera (Coleoptera), for example, furniture death watch beetle (Anobium punctatum), lesser grain borer (Rhizopertha dominica), dislike bar bean weevil (Bruchidius obtectus), acanthoscelides obtectus (Acanthoscelides obtectus), North America house longhorn beetle (Hylotrupes bajulus), willow firefly chrysomelid (Agelastica alni), colorado potato bug (Leptinotarsadecemlineata), horseradish daikon leaf beetle (Phaedon cochleariae), chrysomelid genus (Diabrotica spp.), rape golden head flea beetle (Psylliodes chrysocephala), the large Epilachna spp of Mexico (Epilachna varivestis), Atomaria spp., saw-toothed grain beetle (Oryzaephilus surinamensis), flower resembles genus (Anthonomus spp.), grain weevil belongs to (Sitophilus spp.), black grape ear image (Otiorrhynchus sulcatus), banana collar resembles (Cosmopolites sordidus), Chinese cabbage seed tortoise resembles (Ceuthorrhynchus assimilis), alfalfa leaf resembles (Hypera postica), khapra beetle belongs to (Dermestes spp.), spot khapra beetle belongs to (Trogoderma spp.), Anthrenus (Anthrenus spp.), moth-eaten belong to (the Attagenus spp.) of fur, moth-eaten belong to (the Lyctus spp.) of powder, pollen beetle (Meligethes aeneus), Ptinus (Ptinuss pp.), golden spider beetle (Niptus hololeucus), globose spider beetle (Gibbium psylloides), Tribolium (Tribolium spp.), tenebrio molitor (Tenebrio molitor), click beetle belongs to (Agriotes spp.), wide chest Agriotes spp (Conoderus spp.), the west melolonthid in May (Melolontha melolontha), the potato melolonthid (Amphimallon solstitialis), the brown New Zealand rib wing melolonthid (Costelytra zealandica), rice root weevil (Lissorhoptrus oryzophilus).
Hymenoptera (Hymenoptera), for example, Diprion (Diprion spp.), real tenthredinidae (Hoplocampa spp.), hair ant belong to (Lasius spp.), MonomoriumMayr (Monomorium pharaonis), Vespa (Vespa spp.).
Diptera (Diptera), for example, Aedes (Aedes spp.), Anopheles (Anopheles spp.), Culex (Culex spp.), black-tailed fruit flies (Drosophila melanogaster), Musca (Musca spp.), Fannia (Fannia spp.), calliphora erythrocephala (Calliphora erythrocephala), Lucilia (Lucilia spp.), Carysomyia (Chrysomyia spp.), Cuterebra (Cuterebra spp.), Gasterophilus (Gastrophilus spp.), Hyppobosca spp., Genus Stomoxys (Stomoxys spp.), Oestrus (Oestrus spp.), Hypoderma (Hypoderma spp.), Gadfly (Tabanus spp.), Tannia spp., Bibio hortulanus, Oscinella frit (Oscinella frit), Phorbia (Phorbia spp.), lamb's-quarters spring fly (Pegomyia hyoscyami), Mediterranean Sea Ceratitis spp (Ceratitis capitata), the large trypetid of olive (Dacus oleae), Europe daddy-longlegs (Tipula paludosa), Hylemyia (Hylemyia spp.), Liriomyza (Liriomyza spp.).
Siphonaptera (Siphonaptera), for example, Xanthopsyllacheopis (Xenopsylla cheopis), Ceratophyllus (Ceratophylluss pp.).
Arachnida (Arachnida), for example, Middle East gold scorpion (Scorpio maurus), latrodectus mactans (Latrodectus mactans), Acarus siro (Acarus siro), Argas (Argas spp.), Ornithodoros (Ornithodoros spp.), Dermanyssus gallinae (Dermanyssus gallinae), tea Fischer goitre mite (Eriophyes ribis), the tangerine rust mite (Phyllocoptruta oleivora) that rues, Boophilus (Boophilus spp.), Rh (Rhipicephalus spp.), Amblyomma (Amblyomma spp.), Hyalomma (Hyalomma spp.), hard tick belongs to (Ixodes spp.), overworked mite belongs to (Psoroptes spp.), Chorioptes (Chorioptes spp.), itch mite belongs to (Sarcoptes spp.), Tarsonemus (Tarsonemus spp.), Bryobia praetiosa (Bryobia praetiosa), Panonychus citri belongs to (Panonychus spp.), Tetranychus (Tetranychus spp.), half Tarsonemus (Hemitarsonemus spp.), short whisker Acarapis (Brevipalpus spp.).
Plant nematode comprises, for example, Pratylenchidae belongs to (Pratylenchus spp.), similar similes thorne (Radopholus similis), fuller's teasel Ditylenchus dipsaci (Ditylenchus dipsaci), the nematode (Tylenchulussemipenetrans) of partly puncturing, Heterodera (Heterodera spp.), ball Heterodera (Globodera spp.), Meloidogyne (Meloidogyne spp.), Aphelenchoides (Aphelenchoides spp.), minute hand Turbatrix (Longidorus spp.), Xiphinema (Xiphinema spp.), burr Turbatrix (Trichodorus spp.), Bursaphelenchus (Bursaphelenchus spp.).
If suitable, all right finite concentration of compound of the present invention or rate of application are as weedicide and microbicide, for example, as mycocide, anti-mycotic agent and bactericide.If suitable, they also can be used as intermediate or the precursor of synthetic other active compounds.
All plants and plant parts all can be processed according to the present invention.In the present invention, the implication of plant is interpreted as all plants and plant population, for example need with unwanted wild plant or farm crop (comprising the farm crop that nature exists).Farm crop can be by conventional plant breeding and optimum seeking method or the plant that obtains by biotechnology and recombination method or the combination by described method, comprise transgenic plant, also comprise the plant cultivars that is subject to the protection of plant seedling power or is not subject to its protection.The implication of plant parts is interpreted as all grounds of plant and underground position and organ, for example bud, leaf, Hua Hegen, the example that can mention is leaf, needle, stem, dry, flower, sporophore (fruit-body), fruit, seed, root, stem tuber and rhizome.Plant parts also comprises harvested material, and asexual and sexual propagation thing, for example rice shoot, stem tuber, rhizome, cutting and seed.
The processing that use active compound of the present invention carries out plant and plant parts, by conventional treatment method, directly carry out or make compound effects in surrounding environment, environment or storage space, described conventional treatment method for example soaks, spraying, evaporation, atomizing (fogging), broadcast sowing, smear (painting-on) injection, at breeding thing, particularly seed in the situation that, also can be coated with one or more layers.
Active compound can be converted into conventional formulation, for example solution, emulsion, wettable powder, suspension agent, pulvis, powder agent, paste, soluble powder, granule, outstanding newborn enriching agent, with the microcapsule in active compound impregnated natural and synthetics and polymkeric substance.
Described preparation is prepared in a known way, for example, active compound is mixed with weighting agent, mixes with liquid solvent and/or solid carrier, simultaneously alternative tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or the whipping agent of using.
If the weighting agent using is water, also can, for example, with an organic solvent as solubility promoter.Below be substantially suitable for use as liquid solvent: aromatics, for example dimethylbenzene, toluene or alkylnaphthalene; Chlorination aromatics or chlorinated aliphatic, for example chlorobenzene, vinylchlorid or methylene dichloride; Aliphatic hydrocarbon, for example hexanaphthene or paraffin, as mineral oil fractions, mineral oil and vegetables oil; Alcohol, for example butanols or ethylene glycol and ether thereof and ester; Ketone, for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Intensive polar solvent, for example dimethyl formamide and dimethyl sulfoxide (DMSO), or water.
Applicable solid carrier is:
For example for example kaolin, clay, talcum powder, chalk, quartz, attapulgite, montmorillonite or diatomite of the natural mineral of ammonium salt and pulverizing, and the synthetic materials of pulverizing is silicon-dioxide, aluminum oxide and the silicate of high dispersing for example; The solid carrier that is suitable for granule has: for example pulverize and the natural rock of classification for example calcite, marble, float stone, sepiolite and rhombspar, or synthetic inorganic and organic powder particles, and organic materials particle for example wood sawdust, coconut husk, corn cob and tobacco stem; Applicable emulsifying agent and/or whipping agent have: for example polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate or protein hydrolyzate of nonionic and anionic emulsifier for example; Applicable dispersion agent has: for example lignin sulfite waste lye and methylcellulose gum.
In preparation, can use tackifier, the natural and synthetic polymer of carboxymethyl cellulose and powder, particle or latex shape for example, for example Sudan Gum-arabic, polyvinyl alcohol and polyvinyl acetate, or natural phospholipid for example kephalin and Yelkin TTS and synthetic phospholipid.Other additives can be mineral oil and vegetables oil.
Can use tinting material, for example mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic colorant for example alizarin tinting material, azo colouring agent and metal phthalocyanine tinting material, and micro-nutrients for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Described preparation generally comprises 0.1 to 95 % by weight, the preferred active compound of 0.5 to 90 % by weight.
Active compound of the present invention also can itself or its preparation form mix use with known mycocide, bactericide, miticide, nematocides or insecticide, for example widen in this way action spectrum or prevent resistance.Produce in many cases synergistic effect, the activity of mixture surpasses the activity of each single component.
The compound that is suitable as mixing material standed for has, for example following multiple:
Mycocide:
2-phenylphenol, oxine vitriol, acibenzolar-S-methyl, aldimorph, amidoflumet, ammonia propyl-phosphine acid (ampropylfos), ammonia propyl-phosphine acid potassium, andoprim, anilazine (anilazine), penta ring azoles (azaconazole), nitrile Azoxystrobin (azoxystrobin), M 9834 (benalaxyl), benodanil (benodanil), F-1991 (benomyl), sec.-propyl-benthiavalicarb, benzyl olefin(e) acid (benzamacril), isobutyl-benzyl olefin(e) acid, bialaphos (bilanafos), Niagara 9044 (binapacryl), biphenyl, Bitertanol (bitertanol), miewensu (blasticidin-S), bromuconazole (bromuconazole), the phonetic bacterium spirit of sulphur (bupirimate), powder fixed (buthiobate), butylamine, poly-sulfurated lime, capsimycin (capsimycin), Difolatan (captafol), Vancide 89 (captan), derosal (carbendazim), carboxin (carboxin), carpropamide (carpropamid), Karvon (carvone), chinomethionate (chinomethionat), the pest of going out azoles (chlobenthiazone), benzene imidazoles bacterium (chlorfenazole), chloroneb (chloroneb), m-tetrachlorophthalodinitrile (chlorothalonil), chlozolinate (chlozolinate), clozylacon, cyazofamid (cyazofamid), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), cyproconazole (cyproconazole), cyprodinil (cyprodinil), cyprofuram (cyprofuram), Dagger G, two ethoxy imidazoles prestige (debacarb), Pecudin (dichlofluanid), dichlone (dichlone), dichlorophen (dichlorophen), diclocymet, diclomezine (diclomezine), dicloran (dicloran), the mould prestige of second (diethofencarb), Difenoconazole (difenoconazole), fluorine mepanipyrim (diflumetorim), Milcurb (dimethirimol), dimethomorph (dimethomorph), dimoxystrobin, alkene azoles alcohol (diniconazole), alkene azoles alcohol-M (diniconazole-M), dinocap (dinocap), pentanoic (diphenylamine), Dipyrithione (dipyrithione), ditalimfos (ditalimfos), dithianon (dithianon), dodine, drazoxolon (drazoxolon), Hinosan (edifenphos), oxole bacterium (epoxiconazole), Han Lening (ethaboxam), Milstem (ethirimol), Truban (etridiazole), azolactone bacterium (famoxadone), fenamidone (fenamidone), fenapanil (fenapanil), fenarimol (fenarimol), RH-7592 (fenbuconazole), first furan is drunk aniline (fenfuram), fenhexamid (fenhexamid), plant clothing ester (fenitropan), fenoxanil (fenoxanil), fenpiclonil (fenpiclonil), fenpropidin (fenpropidin), fenpropimorph (fenpropimorph), Karbam Black (ferbam), fluazinam (fluazinam), flubenzimine, Fu Evil bacterium (fludioxonil), fluorine biphenyl bacterium (flumetover), flumorph (flumorph), fluoromide (fluoromide), fluoxastrobin (fluoxastrobin), Fluquinconazole (fluquinconazole), flurprimidol (flurprimidol), fluzilazol (flusilazole), flusulfamide (flusulfamide), fultolanil (flutolanil), flutriafol (flutriafol), Phaltan (folpet), fosetyl (fosetyl-Al), fosetyl sodium (fosetyl-sodium), fuberidazole (fuberidazole), Furalaxyl (furalaxyl), furan pyrazoles spirit (furametpyr), sterilizing amine (furcarbanil), seed dressing amine (furmecyclox), Guanoctine (guazatine), Perchlorobenzene (hexachlorobenzene), own azoles alcohol (hexaconazole), hymexazol (hymexazole), IMAZALIL (imazalil), acid amides azoles (imibenconazole), biguanide spicy acid salt (iminoctadine triacetate), biguanide spicy acid salt (iminoctadine tris (albesil)), iodocarb, cycltebuconazole (ipconazole), iprobenfos (iprobenfos), isopropyl fixed (iprodione), iprovalicarb (iprovalicarb), people's metamycin (irumamycin), isoprothiolane (isoprothiolane), chlorobenzene climbazole (isovaledione), kasugamycin (kasugamycin), imines bacterium (kresoxim-methyl), zinc manganese ethylenebisdithiocarbamate (mancozeb), maneb (maneb), meferimzone, mepanipyrim (mepanipyrim), the third oxygen mebenil (mepronil), metaxanin (metalaxyl), Metalaxyl-M (metalaxyl-M), encircle penta azoles bacterium (metconazole), methasulfocarb (methasulfocarb), first methuroxam (methfuroxam), Carbatene (metiram), fork phenalgin acid amides (metominostrobin), metsulfovax (metsulfovax), midolthromycin (mildiomycin), nitrile bacterium azoles (myclobutanil), myclozolin (myclozolin), myprozine (natamycin), nicobifen, isopropyl disappear (nitrothal-isopropyl), noviflumuron, nuarimol (nuarimol), fenfuram (ofurace), orysastrobin, Evil frost spirit (oxadixyl), oxolinic acide (oxolinic acid), oxpoconazole, oxycarboxin (oxycarboxin), oxyfenthiin, paclobutrazol (paclobutrazol), pefurazoate (pefurazoate), Topaze (penconazole), pencycuron (pencycuron), two S-sevens (phosdiphen), phthalide (phthalide), ZEN 90160 (picoxystrobin), pipron (piperalin), polyoxin (polyoxins), polyoxorim, thiabendazole (probenazole), Prochloraz (prochloraz), sterilization profit (procymidone), hundred dimension spirits (propamocarb), propanosine-sodium, Wocosin 50TK (propiconazole), zinc 1,2-propylene bisdithiocarbamate (propineb), proquinazid, prothioconazole, pyraclostrobin (pyraclostrobin), pyrazophos (pyrazophos), pyrifenox (pyrifenox), pyrimethanil (pyrimethanil), pyroquilon (pyroquilon), chlorine pyrrole furan ether (pyroxyfur), pyrrolenitrine, azoles oxolinic acide (quinconazole), quinoxyfen (quinoxyfen), quintozene (quintozene), simeconazoles (simeconazole), the luxuriant amine of Luo Evil (spiroxamine), sulphur, tebuconazole (tebuconazole), tecloftalam (tecloftalam), tecnazene (tecnazene), tetcyclacis, fluorine ether azoles (tetraconazole), Apl-Luster (thiabendazole), thicyofen (thicyofen), thifluzamide (thifluzamide), thiophanate methyl (thiophanate-methyl), thiram (thiram), tioxymid, tolclofosmethyl (tolclofos-methyl), tolylfluanid (tolylfluanid), triazolone (triadimefon), Triabimeno I (triadimenol), fourth triazole (triazbutil), azoles bacterium piperazine (triazoxide), tricyclamide, tricyclazole (tricyclazole), tridemorph (tridemorph), oxime bacterium ester (trifloxystrobin), fluorine bacterium azoles (triflumizole), triforine (triforine), triticonazole (triticonazole), uniconazole (uniconazole), Validacin (Takeda) (validamycin A), vinclozolin (vinclozolin), zineb (zineb), ziram (ziram), zoxamide (zoxamide), (2S)-N-[2-[4-[[3-(4-chloro-phenyl-)-2-propynyl] oxygen]-3-p-methoxy-phenyl] ethyl]-3-methyl-2-[(methyl sulphonyl) amino] butyramide, 1-(1-naphthyl)-1H-pyrroles-2,5-diketone, 2,3,5,6-tetrachloro-4-(methyl sulphonyl) pyridine, 2-amino-4-methyl-N-phenyl-5-thiazole carboxamides, the chloro-N-of 2-(2,3-dihydro-1,1,3-trimethylammonium-1H-indenes-4-yl)-Niacinamide, 3,4,5-tri-is chloro-2,6-pyridine dintrile, actinovate, cis-1-(4-chloro-phenyl-)-2-(1H-1,2,4-triazol-1-yl) suberyl alcohol, 1-(2,3-dihydro-2,2-dimethyl-1H-indenes-1-yl)-1H-imidazole-5-carboxylic acid methyl esters, saleratus, N-(6-methoxyl group-3-pyridyl) cyclopropane carboxamide, N-butyl-8-(1,1-dimethyl ethyl)-1-oxaspiro [4.5] decane-3-amine, tetrathio sodium carbonate,
Also have mantoquita and preparation thereof, for example Bordeaux mixture, copper hydroxide, copper naphthenate, COPPER OXYCHLORIDE 37,5 (copper oxychloride), copper sulfate, cufraneb (cufraneb), Red copper oxide, mancopper (mancopper), oxinecopper (oxine-copper).
Bactericide:
Bronopol (bronopol), dichlorophen, nitrapyrin (nitrapyrin), nickel dimethyldithiocarbamate (nickel-dimethyldithiocarbamate), kasugamycin, different thiophene bacterium ketone (octhilinone), carboxylic acid furans (furancarboxylic acid), terramycin (oxytetracyclin), thiabendazole, Streptomycin sulphate (streptomycin), tecloftalam, copper sulfate and other copper agents.
Insecticide/miticide/nematocides:
Avermectin (abamectin), ABG-9008, Ortho 12420 (acephate), acequinocyl (acequinocyl), pyrrole worm clear (acetamiprid), second phthalein worm eyeball (acetoprole), fluorine ester chrysanthemum ester (acrinathrin), AKD-1022, AKD-3059, AKD-3088, alanycarb (alanycarb), aldicarb (aldicarb), the sulfone prestige (aldoxycarb) of going out, Pynamin (allethrin), nail body Cypermethrin (alpha-cypermethrin, alphamethrin), amidoflumet, aminocarb (aminocarb), U-36059 (amitraz), Avrmectin (avermectin), AZ-60541, Ai Zhading (azadirachtin), azoles pyridine phosphorus (azamethiphos), R-1582 (azinphos-methyl), triazotion (azinphos-ethyl), azoles ring tin (azocyclotin),
Bacillus popilliae (Bacillus popilliae), Bacillus sphaericus (Bacillus sphaericus), Ke opposes gram bacterium (Bacillus subtilis), Bacillus thuringiensis (Bacillus thuringiensis), Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, baculovirus (baculoviruses), beauveria bassiana (Beauveria bassiana), beauveria tenella (Beauveria tenella), benclothiaz, Evil worm prestige (bendiocarb), benfuracarb (benfuracarb), bensultap (bensultap), benzoximate (benzoximate), β-cyfloxylate (beta-cyfluthrin), Cypermethrin (beta-cypermethrin), Bifenazate (bifenazate), bifenthrin (bifenthrin), Niagara 9044, Dtrans allethrin (bioallethrin), Dtrans allethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin (biopermethrin), bioresmethrin (bioresmethrin), bistrifluron (bistrifluron), BPMC, brofenprox, bromophos_ethyl (bromophos-ethyl), bromopropylate (bromopropylate), bromobenzene alkene phosphorus (methyl) (bromfenvinfos (methyl)), BTG-504, BTG-505, bufencarb (bufencarb), Buprofezin (buprofezin), special Pyrimitate (butathiofos), fourth fork prestige (butocarboxim), oxygen fourth fork prestige (butoxycarboxim), butyl pyridaben (butylpyridaben),
Cadusafos (cadusafos), toxaphene (camphechlor), SevinCarbaryl (carbaryl), carbofuran (carbofuran), carbophenothion (carbophenothion), carbosulfan (carbosulfan), Padan (cartap), CGA-50439, chinomethionate (chinomethionat), Niran (chlordane), chlordimeform (chlordimeform), chloethocarb, earth worm chlorine phosphorus (chlorethoxyfos), fluorine azoles worm clear (chlorfenapyr), Zaprawa enolofos (chlorfenvinphos), UC 62644 (chlorfluazuron), chlormephos (chlormephos), G-23922 (chlorobenzilate), trichloronitromethane (chloropicrin), chlorproxyfen, chlorpyrifos_methyl (chlorpyrifos-methyl), Chlorpyrifos 94 (ethyl), chlovaporthrin, ring worm hydrazides (chromafenozide), cis-Cypermethrin, cis-Chryson (cis-resmethrin), cis-permethrin (cis-permethrin), cyhalothrin (clocythrin), cloethocarb (cloethocarb), clofentezine (clofentezine), clothianidin (clothianidin), clothiazoben, Pherocon CM (codlemone), Coumaphos (coumaphos), S-4087 (cyanofenphos), cynock (cyanophos), cycloprene, cycloprothrin (cycloprothrin), Cydia pomonella, cyfloxylate (cyfluthrin), (RS) cyhalothrin (cyhalothrin), cyhexatin (cyhexatin), Cypermethrin (cypermethrin), phenylate permethrin (1R-trans-isomer(ide)) (cyphenothrin (1R-trans isomer)), cyromazine (cyromazine),
DDT, Deltamethrin (deltamethrin), methyl 1 (demeton-S-methyl), dioxydemeton-s-methyl (demeton-S-methylsulfone), kill mite sulphur grand (diafenthiuron), torak (dialifos), diazinon (diazinon), dichlofenthion (dichlofenthion), SD-1750 (dichlorvos), Mitigan (dicofol), Carbicron (dicrotophos), Dicyclanil (dicyclanil), TH-6040 (diflubenzuron), dimefluthrin, Rogor (dimethoate), dimethylvinphos (dimethylvinphos), dinobuton (dinobuton), dinocap (dinocap), MTI-446 (dinotefuran), the luxuriant ether of Evil (diofenolan), thiodemeton (disulfoton), iodoxy fourth two pungent (docusat-sodium), benzene oxycetylene mite (dofenapyn), DOWCO-439, eflusilanate, emaricin (emamectin), emaricin benzoate (emamectin-benzoate), Prallethrin (1R isomer) (empenthrin (1Risomer)), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), entomophthora belongs to kind of (an Entomopthora spp.), EPN, esfenvalerate (esfenvalerate), benzene worm prestige (ethiofencarb), ethiprole (ethiprole), Nialate (ethion), ethoprop (ethoprophos), ether chrysanthemum ester (etofenprox), Te Ben oxazole (etoxazole), oxygen Pyrimithate (etrimfos),
Famophos (famphur), Nemacur (fenamiphos), fenazaquin (fenazaquin), fenbutatin oxide (fenbutatin oxide), fenfluthrin (fenfluthrin), Sumithion (fenitrothion), Osbac (fenobucarb), fenothiocarb (fenothiocarb), fenoxacrim, ABG-6215 (fenoxycarb), Fenvalerate (fenpropathrin), must mite Garrick (fenpyrad), fenpirithrin (fenpyrithrin), fenpyroximate (fenpyroximate), fensulfothion (fensulfothion), Tiguvon (fenthion), fluorine nitre pentanoic (fentrifanil), kill chrysanthemum ester (fenvalerate), Frontline (fipronil), flonicamid (flonicamid), fluacrypyrim, fluorine fluazuron (fluazuron), thiazole mite (flubenzimine), brofluthrinate (flubrocythrinate), flucycloxuron (flucycloxuron), flucythrinate (flucythrinate), flufenerim, flufenoxuron (flufenoxuron), fluorine the third benzyl oxide (flufenprox), flumethrin (flumethrin), pyrrole fluorine sulphur phosphorus (flupyrazofos), flutiazin (flutenzin) (fluorine mite piperazine (flufenzine)), taufluvalinate (fluvalinate), Dyfonate (fonofos), formetanate (formetanate), peace fruit (formothion), fosmethilan (fosmethilan), thiazolone phosphorus (fosthiazate), fubfenprox (halfenprox (fluproxyfen)), furathiocarb (furathiocarb),
Gamma-cyhalothrin, lindane (gamma-HCH), gossyplure (gossyplure), Grandemone (grandlure), granulosis virus(GV) (granuloviruses),
Halogen ether chrysanthemum ester (halfenprox), RH 0345 (halofenozide), HCH, HCN-801, worm phosphorus in heptan (heptenophos), HEXAFLUMURON (hexaflumuron), hexythiazox (hexythiazox), amdro (hydramethylnone), Entocon ZR 512 (hydroprene),
IKA-2002, imidacloprid (imidacloprid), Imiprothrin (imiprothrin), oxadiazole worm (indoxacarb), iodfenphos TOP (iodofenphos), iprobenfos (iprobenfos), fluorine azoles phosphorus (isazofos), propylamine phosphorus (isofenphos), isoprocarb (isoprocarb), isoxazoline (isoxathion), ivermectin (ivermectin),
japonilure、
Sai Evil chrysanthemum ester (kadethrin), nucleopolyhedrosis virus (nuclear polyhedrosis virus), cover 7 (kinoprene),
Cyhalothrin (lamda-cyhalothrin), lindane (lindane), fluorine the third oxygen urea (lufenuron),
Phosphothion (malathion), mecarbam (mecarbam), first oxydemeton_methyl (mesulfenfos), Halizan (metaldehyde), metamsodium (metam-sodium), methacrifos (methacrifos), acephatemet (methamidophos), green muscardine fungus (Metharhizium anisopliae), yellowish green green muscardine fungus (Metharhizium flavoviride), methidathion (methidathion), metmercapturon (methiocarb), methomyl (methomyl), Entocon ZR 515 (methoprene), methoxychlor (methoxychlor), Runner (methoxyfenozide), metofluthrin, meta-tolyl-N-methylcarbamate (MTMC) (metolcarb), metoxadiazone (metoxadiazone), Phosdrin (mevinphos), milbemycin (milbemectin), milbemycin (milbemycin), MKI-245, MON-45700, monocrotophos (monocrotophos), Moxidectin (moxidectin), MTI-800,
Naled (naled), NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide (niclosamide), nicotine (nicotine), nitenpyram (nitenpyram), WL 35651 (nithiazine), NNI-0001, NNI-0101, NNI-0250, NN I-9768, Rimon (novaluron), noviflumuron (noviflumuron),
OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate (omethoate), thioxamyl (oxamyl), oxydemeton methyl (oxydemeton-methyl),
Paecilomyces fumosoroseus (Paecilomyces fumosoroseus), methyl parathion (parathion methyl), one six zero five (ethyls), permethrin is (cis-, trans-), oil, PH-6045, phenothrin (1R trans-isomer(ide)) (phenothrin (1R-transisomer), Tsidial (phenthoate), phorate (phorate), zolone (phosalone), R-1504 (phosmet), phosphamidon (phosphamidon), second the third phosphorus prestige (phosphocarb), phoxim (phoxim), piperonyl butoxide (piperonyl butoxide), Aphox (pirimicarb), pirimiphosmethyl (pirimiphos methyl), pirimiphos ethyl (pirimiphos-ethyl), potassium oleate, prallethrin (prallethrin), Profenofos (profenofos), profluthrin, promecarb (promecarb), Kayaphos (propaphos), propargite (propargite), propetamphos (propetamphos), Propoxur (propoxur), Toyodan (prothiofos), Fac (prothoate), protrifenbute, pymetrozine (pymetrozine), pyraclofos (pyraclofos), anti-Chryson (pyresmethrin), pyrethrum (pyrethrum), pyridaben (pyridaben), pyridalyl (pyridalyl), Ofunack (pyridaphenthion), pyridathion, pyramine phenylate (pyrimidifen), pyriproxyfen (pyriproxyfen),
Quinalphos (quinalphos),
Chryson, RH-5849, ribavirin (ribavirin), RU-12457, RU-15525,
S-421, S-1833, salithion (salithion), cadusafos (sebufos), SI-0009, deinsectization silicon ether (silafluofen), spinosad (spinosad), spiral shell mite ester (spirodiclofen), Spiromesifen (spiromesifen), sulfluramid (sulfluramid), dithione (sulfotep), second Toyodan (sulprofos), SZI-121,
Taufluvalinate (tau-fluvalinate), RH-5992 (tebufenozide), tebufenpyrad (tebufenpyrad), Tebupirimphos (tebupirimphos), volt worm phosphorus (teflubenzuron), tefluthrin (tefluthrin), temephos (temephos), deinsectization fear (temivinphos), terbam (terbam), Terbufos (terbufos), tetrachlorvinphos (tetrachlorvinphos), tetradifon (tetradifon), Tetramethrin (tetramethrin), Tetramethrin (1R isomer), Diphenylsulfide (tetrasul), pungent body Cypermethrin (theta-cypermethrin), thiacloprid (thiacloprid), Diacloden (thiamethoxam), moth fly nitrile (thiapronil), thiatriphos, thiocyclarn (thiocyclam hydrogen oxalate), UC-51762 (thiodicarb), special ammonia fork prestige (thiofanox), thiometon (thiometon), disosultap (thiosultap-sodium), thuringiensin (thuringiensin), tolfenpyrad, fluorine Deltamethrin (tralocythrin), tralomethrin (tralomethrin), transfluthrin (transfluthrin), benzene match mite (triarathene), triaxamate (triazamate), triazophos (triazophos), triazuron, trichlophenidine, Trichlorphon (trichlorfon), Trichoderma atroviride, desinsection grand (triflumuron), trimethacarb (trimethacarb),
Vamidothion (vamidothion), fluorine pyrazoles worm (vaniliprole), verbutin, Verticillium lecanii (Verticillium lecanii),
WL-108477、WL-40027、
YI-5201、YI-5301、YI-5302、
XMC, xylylcarb (xylylcarb),
ZA-3274, own body Cypermethrin (zeta-cypermethrin), zolaprofos, ZXI-8901,
Compound 3-aminomethyl phenyl carboxylamine propyl ester (meta-tolyl-N-methylcarbamate (MTMC) Z (tsumacide Z)),
Compound 3-(5-chloro-3-pyridyl base)-8-(2,2,2-trifluoroethyl)-8-azabicyclo [3.2.1] octane-3-nitrile (CAS number of registration 185982-80-3) and corresponding 3-endo isomer (CAS number of registration 185984-60-5) (referring to WO-96/37494, WO-98/25923),
And include the preparation that kills insect active plant milk extract, nematode, fungi or virus.
Active compound that also can be known with other, weedicide for example, or mix with fertilizer and growth regulator, safener and/or semiochemicals.
The type of service of preparing with Huo You commercial preparation, commercial preparation is when the insecticide, and active compound of the present invention can be further exists with the form of the mixture with synergistic agent.Synergistic agent is for improving active itself the activated compound of tool not necessarily of active compound.
When the type of service of preparing with Huo You commercial preparation, commercial preparation is used as insecticide, active compound of the present invention can be further exists with the form of the mixture with inhibitor, and described inhibitor can reduce the degraded of active compound after using in habitat, plant parts surface or the plant tissue of plant.
The compounds content of the type of service of being prepared by commercial preparation can change in wider scope.The activity compound concentration of type of service can be 0.0000001 to 95 % by weight, the preferred active compound of 0.0001 to 1 % by weight.
They are used to be suitable for the usual manner of type of service.
When being used for resisting sanitary insect pest (hygiene pest) and storing Product Pests, active compound is being had outstanding performance aspect following two: i.e. good residual activity on timber and clay, and the well tolerable property to the alkali in lime matrix.
As mentioned above, can process all plants or its position according to the present invention.In preferred embodiments, processed wild plant kind or by conventional Biology Breeding method, for example, by hybridizing or botanical variety that protoplast fusion obtains and the position of plant cultivars and described mutation and cultivar.In more preferred, if processed transgenic plant and plant cultivars and the position thereof being obtained by suitable also can the combining with ordinary method (biology of genetic modification (genetically modified organism)) of recombination method.Term " position " or " position of plant " or " plant parts " are explained as above.
The plant of particularly preferably processing according to the present invention is the commercially available or plant cultivars used separately.The implication of plant cultivars is interpreted as the plant with new features (" feature ") by conventional breeding, mutagenesis or recombinant DNA technology breeding.They can be cultivar, biotype (biotype) and genotype form.
According to plant species or plant cultivars, its plantation place and growth conditions (soil, weather, vegetation period, nutrition (nutrition)), processing of the present invention also can produce superadditivity (superadditive) (" collaborative ") effect.Thus, for example can reduce rate of application and/or widen action spectrum and/or improve the material that can use by the present invention and the activity of composition, improve plant-growth, improve high temperature or cold tolerance, raising arid or water or soil salt content tolerance, improve Flowering quality, make to gather simpler and easy, accelerates maturing, raising output, improve the quality of the product of gathering and/or improve its nutritive value, improve Storage property and/or its processing characteristics of the product of gathering, these can surpass the effect of actual desired.
Transgenic plant or plant cultivars (obtaining by recombination method) that preferred the present invention processes are included in all plants of accepting genetic material in recombinant modified, and described genetic material is given described plant by particularly advantageous useful property (" feature ").The example of described characteristic is to improve plant-growth, improve high temperature or cold tolerance, raising arid or water or soil salt content tolerance, improve Flowering quality, make to gather simpler and easy, accelerates maturing, raising output, improve the quality of the product of gathering and/or improve its nutritive value, improve Storage property and/or its processing characteristics of the product of gathering.Other examples of the described characteristic that need mention especially are to improve the resistibility of plant to animal and microorganism insect, for example, to insect, acarid, phytopathogenic fungi, bacterium and/or virus, and improve the tolerance of plant to some weeding active compound.The example of the transgenic plant that can mention is important crop plants, such as grain (wheat, rice), corn, soybean, potato, cotton, tobacco, rape (oilseed rape) and fruit tree (fruit is apple, pears, citrus fruits and grape), ben is corn, soybean, potato, cotton, tobacco and rape.Ben characteristic (" feature ") is for by form toxin in plant materials, particularly for example, by genetic material (gene C ry I A (a), Cry I A (b), Cry I A (c), Cry II A, Cry III A, Cry III B2, Cry 9c Cry 2Ab, Cry 3Bb and Cry I F and the combination thereof of Bacillus thuringiensis; Be designated hereinafter simply as " Bt plant ") toxin that forms in plant materials, improves the resistibility of plant to insect, arachnid, nematode and snail (slugs and snails).Ben other characteristics (" feature ") are for improving plant to fungi, bacterium and viral resistibility by systemic acquired resistance (SAR), systemin, phytoalexin, releaser and resistant gene and corresponding marking protein and toxin.Other characteristics that stress in particular (" feature ") for example, for example, for improving the tolerance of plant to some weeding active compound, imidazolone type, sulfonylurea, glyphosate (glyphosate) or phosphinotricin (" PAT " gene).Give required characteristic (" feature ") but gene also in each comfortable transgenic plant body, mutually combine.The example of " the Bt plant " that can mention is that commercially available trade(brand)name is YIELD (for example corn, cotton, soybean), (for example corn), (for example corn), (cotton), (cotton) and the maize culture kind of (potato), culture of cotton kind, soybean culture kind and Potato cultivar.The example of the plant with herbicide tolerant that can mention is that commercially available trade(brand)name is Roundup (thering is glyphosate tolerance, for example corn, cotton, soybean), Liberty (thering is phosphinotricin tolerance, for example rape), (thering is imidazolinone-tolerant) and the maize culture kind of (thering is sulfonylurea tolerance, for example corn), culture of cotton kind and soybean culture kind.The plant with Herbicid resistant that can mention (with the plant of conventional herbicide tolerant mode breeding) also comprises commercially available cultivar (for example corn).Certainly, above narration is also applicable to have the plant cultivars of genetic characteristics described or leaved for development (" feature "), and described plant cultivars will be developed and/or go on the market in future.
Particularly advantageously, described plant can be processed according to general formula of the present invention (I) compound or active compound combinations for the present invention.The preferable range of above-mentioned active compound and mixture is also applicable to the processing of described plant.Ben is that compound or the mixture of mentioning especially with the present invention processed plant.
Active compound of the present invention not only has activity to plant insect, sanitary insect pest and storage Product Pests, and in veterinary applications for example, to zooparasite (vermin), hard tick, soft ticks, itch mite, harvest mite, fly (bite and suck), tachinid larva, lice, hair lice, poultry louse and flea also have activity.Described parasite comprises:
Anoplura (Anoplurida), for example, Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), lice belong to (Pediculus spp.), Phtirus spp., pipe lice belongs to (Solenopotes spp.).
Mallophaga (Mallophagida) and Amblycera (Amblycerina) and thin angle suborder (Ischnocerina), for example, hair Trichodectes (Trimenopon spp.), Menopon (Menopon spp.), huge Trichodectes (Trinoton spp.), Bovicola (Bovicola spp.), Werneckiella spp., Lepikentron spp., Damalinia (Damalina spp.), Trichodectes (Trichodectes spp.), Felicola (Felicola spp.).
Diptera and Nemocera (Nematocerina) and Brachycera (Brachycerina), for example, Aedes (Aedes spp.), Anopheles (Anopheles spp.), Culex (Culex spp.), Simulium (Simulium spp.), Eusimulium (Eusimulium spp.), owl midge (Phlebotomus spp.), Lutzomyia (Lutzomyia spp.), Bitting midge (Culicoides spp.), Chrysops (Chrysops spp.), knurl Gadfly (Hybomitra spp.), Atylotus (Atylotus spp.), Gadfly (Tabanus spp.), Chrysozona (Haematopota spp.), Philipomyia spp., honeybee Hippobosca (Braula spp.), Musca (Musca spp.), Hydrotaea (Hydrotaea spp.), Genus Stomoxys (Stomoxys spp.), Haematobia (Haematobia spp.), fly does not belong to (Morellia spp.), Fannia (Fannia spp.), Glossina (Glossina spp.), Calliphora (Calliphora spp.), Lucilia (Lucilia spp.), Carysomyia (Chrysomyia spp.), Wohlfahrtia (Wohlfahrtia spp.), Sarcophaga (Sarcophaga spp.), Oestrus (Oestrus spp.), Hypoderma (Hypodermaspp.), Gasterophilus (Gasterophilus spp.), Hippobosca (Hippobosca spp.), Lipoptena (Lipoptena spp.), Melophagus (Melophagus spp.).
Siphonaptera (Siphonapterida), for example, flea belongs to (Pulex spp.), Ctenocephalus (Ctenocephalides spp.), objective flea belongs to (Xenopsylla spp.), Ceratophyllus (Ceratophyllus spp.).
Heteroptera (Heteropterida), for example, Cimex (Cimex spp.), Triatoma (Triatoma spp.), Rhodnius (Rhodnius spp.), Triatoma (Panstrongylus spp.).
Blattodea (Blattarida), for example, oriental cockroach (Blattaorientalis), periplaneta americana (Periplaneta americana), blatta germanica (Blattela germanica), Supella (Supella spp.).
Acari (Acaria or Acarida) and rear valve order (Metastigmate) and Mesostigmata (Mesostigmata), for example, Argas (Argas spp.), Ornithodoros (Ornithodorus spp.), residual beak tick belongs to (Otobius spp.), hard tick belongs to (Ixodes spp.), Amblyomma (Amblyomma spp.), Boophilus (Boophilus spp.), Dermacentor (Dermacentor spp.), Haemophysalis spp., Hyalomma (Hyalomma spp.), Rh (Rhipicephalus spp.), Dermanyssus (Dermanyssus spp.), sting sharp mite and belong to (Raillietia spp.), Pneumonyssus (Pneumonyssus spp.), chest thorn mite belongs to (Sternostoma spp.), Vespacarus (Varroa spp.).
Axle Acarina (Actinedida) (front valve suborder (prostigmata)) and flour mite order (Acaridida) (Astigmata (Astigmata)), for example, honeybee shield mite belongs to (Acarapis spp.), Cheyletiella (Cheyletiella spp.), Ornithocheyletia (Ornithocheyletia spp.), Myobia (Myobia spp.), Psorergates (Psorergates spp.), Demodex (Demodex spp.), Trombidium (Trombicula spp.), Listrophorus spp., Tyroglyphus (Acarus spp.), Tyrophagus (Tyrophagus spp.), Caloglyphus (Caloglyphus spp.), under neck, mite belongs to (Hypodectes spp.), wing mite belongs to (Pterolichus spp.), overworked mite belongs to (Psoroptes spp.), Chorioptes (Chorioptes spp.), ear itch mite belongs to (Otodectes spp.), itch mite belongs to (Sarcoptes spp.), Notoedres (Notoedres spp.), lump mite belongs to (Knemidocoptes spp.), Cytodites (Cytodites spp.), Laminosioptes (Laminosioptes spp.).
Formula of the present invention (I) active compound is also applicable to the arthropods of the agriculture livestock of control invasion and attack, for example attack ox, sheep, goat, horse, pig, donkey, camel, buffalo, rabbit, chicken, turkey, duck, goose, honeybee, other domestic animals, for example dog, cat, cage bird, aquarium fish, and so-called experimental animal, for example hamster, cavy, rat and mouse.By preventing and treating described arthropods, be intended to reduce death and output reduction (meat, milk, hair, skin, egg, honey etc.), thereby active compound that can the application of the invention makes herding more economical, easier.
Active compound of the present invention is in a known way for veterinary applications, can be by for example tablet, capsule, oral potus, preserved material, granule, paste, pill, feed (feed-through) method, the mode of suppository is carried out administration in intestines, can be by for example injection (intramuscular, subcutaneous, vein, intraperitoneal etc.), intestines external administration is carried out in implantation, can nasal administration, can be by for example soaking or embathing, spraying, sprinkle and water, drop, clean, the form of dusting, by means of the moldings that comprises active compound, necklace for example, ear tag, tail tag, limbs ligature (limb band), halter, concentrator markers etc. carry out percutaneous drug delivery.
During for domestic animal, poultry, domestic animal etc., the preparation (for example pulvis, emulsion, suspension concentrate) that formula (I) active compound can be used as the active compound that comprises 1 to 80 % by weight is directly used, also can dilute 100 to 10000 times and uses, or use with chemical Medicatedbath lotion (chemical bath) form afterwards.
And, found that active compound of the present invention has to damaging the insect of Industrial materials the insect active of killing.
Mode with nonrestrictive example can preferably propose following insect:
Beetle, for example
North America house longhorn beetle (Hylotrupes bajulus), Chlorophorus pilosis, furniture death watch beetle (Anobium punctatum), report dead death watch beetle (Xestobium rufovillosum), Ptilinus pectinicornis (Ptilinu specticornis), Dendrobium pertinex, pine death watch beetle (Ernobius mollis), Priobium carpini, Lyctus brunneus Stephens (Lyctus brunneus), Africa powder moth-eaten (Lyctus africanus), south powder moth-eaten (Lyctus planicollis), quercitron moth-eaten (Lyctus linearis), pubescence powder moth-eaten (Lyctus pubescens), Trogoxylon aequale, minthea rugicollis (Minthes rugicollis), material bark beetle kind (Xyleborus spec.), Tryptodendron spec., coffee black long moth-eaten (Apate monachus), Mongolian oak long moth-eaten (Bostrychus capucins), brown different wing long moth-eaten (Heterobostrychus brunneus), long moth-eaten plant (the Sinoxylon spec.) of sour jujube, dinoderus minutus (Dinoderus minutus).
Dermaptera insect (dermapteran), for example
Large wood wasp (Sirex juvencus), the large wood wasp of fir (Urocerus gigas), safe wood wasp (Urocerus gigas taignus), the Urocerus augur of strengthening.
Termite, for example
Europe kalotermitid (Kalotermes flavicollis), a fiber crops heap sand termite (Cryptotermes brevis), ash point different termite (Heterotermes indicola), American-European reticulitermes flavipe (Reticulitermes flavipes), Sang Te reticulitermes flavipe (Reticulitermes santonensis), southern Europe reticulate pattern termite (Reticulitermes lucifugus), Darwin Australia termite (Mastotermes darwiniensis), the ancient termite (Zootermopsis nevadensis) in Nevada, Coptotermes formosanus Shtrari． (Coptotermes formosanus).
Moth (Bristletail), for example silverfish (Lepisma saccharina).
In the present invention, the implication of Industrial materials is interpreted as non-living body (non-live) material, for example, is preferably synthetic materials, tackiness agent, glue, paper and sheet material, leather, timber and Wood products and paint.
To be protectedly to avoid the material of insect infestations, most preferably be timber and Wood products.
Can or comprise that by composition of the present invention the timber of mixture protection of described composition and the implication of Wood products are interpreted as, for example:
Construction timber, wooden frame, railroad tie, bridge module, jetty, the wooden vehicles, case, bracket, freight container, electric pole, wooden coating (wood cladding), wooden doors and windows, glued board, shaving board, joinery or be generally used for house building or the Wood products of construction carpenter.
Active compound can itself or concentrated solution or the form of general conventional formulation use, described dosage form is pulvis, granule, solution, suspension agent, emulsion or paste for example.
Above-mentioned preparation can be prepared in a manner known way, for example active compound and at least one solvent or thinner, emulsifying agent, dispersion agent and/or tackiness agent or fixing agent, water-resisting agent are mixed, if suitable, also can mix with siccative and UV stablizer, and if suitable, also can process auxiliary agent with tinting material and dyestuff and other and mix.
For the protection of insecticidal mixtures or the concentrated solution of timber and wooden materials, comprise that concentration is 0.0001 to 95 % by weight, particularly the active compound of the present invention of 0.001 to 60 % by weight.
The usage quantity of composition or concentrated solution depends on kind and occurrence rate (occurence) and the medium of insect.Optimum rate of application can be respectively by being used and determine in series of experiments.Yet generally speaking, the material based on to be protected, is used 0.0001 to 20 % by weight, preferably the active compound of 0.001 to 10 % by weight is just enough.
The solvent and/or the thinner that use are, organic chemistry solvent or solvent mixture and/or low volatility oily or oil type organic chemistry solvent or solvent mixture and/or polar organic are learned solvent or solvent mixture and/or water, if and suitable, also have emulsifying agent and/or wetting agent.
The organic chemistry solvent preferably using for evaporation number (evaporation number) higher than 35, flash-point higher than 30 ℃, preferably higher than oily or the oil type solvent of 45 ℃.The material that can be used as described water-fast low volatility oily and oil type solvent is applicable mineral oil or its aromaticity cut, or contains the solvent mixture of mineral oil, preferably petroleum solvent, oil and/or alkylbenzene.
The material of favourable use has: the oil that spindle oil, boiling range that petroleum solvent, boiling range that the mineral oil that boiling range is 170 to 220 ℃, boiling range are 170 to 220 ℃ are 250 to 350 ℃ are 160 to 280 ℃ or phenolic compound, turpentine wet goods.
In preferred embodiments, the aromatic hydrocarbon that the liquid fat hydrocarbon that use boiling range is 180 to 210 ℃ or boiling range are 180 to 220 ℃ and high boiling mixture and/or spindle oil and/or the naphthalene monochloride of aliphatic hydrocarbon, preferably α-naphthalene monochloride.
Evaporation number higher than 35, flash-point higher than 30 ℃, preferably higher than the organic oily of low volatility or the oil type solvent of 45 ℃, can partly with high or medium volatile organic chemistry solvent, replace, as long as solvent mixture also have higher than 35 evaporation number and higher than 30 ℃, preferably higher than the flash-point of 45 ℃, and it is solvable or can emulsification in this solvent mixture to kill insect/fungicidal mixtures.
In preferred embodiments, a part for organic chemistry solvent or solvent mixture is replaced by aliphatics polar organic solvent or solvent mixture.The material preferably using is the aliphatics organic chemistry solvent with hydroxyl and/or ester group and/or ether, such as glycol ether, ester etc.
The organic chemistry tackiness agent using within the scope of the present invention for synthetic resins and/or dilutable water and/or can be in the organic chemistry solvent using the own known bonding siccative oil (binding drying oil) of dissolving or dispersion or emulsification, particularly by following material, formed, or comprise the tackiness agent of following material: acrylic resin, Vinylite, polyvinyl acetate for example, vibrin, polycondensation or polyaddition resin, urethane resin, Synolac or modified alkyd resin, phenol resins, hydrocarbon resin, indenes/coumarone resin for example, silicone resin, dry vegetable oil and/or siccative oil and/or the physics dry adhesive based on natural and/or synthetic resins.
As the synthetic resins of tackiness agent can emulsion, dispersion or solution form used.The pitch or the asphaltic substances that are up to 10 % by weight also can be used as tackiness agent.In addition, can known tinting material, pigment, water-resisting agent, mask agent and inhibitor or the inhibitor etc. of use itself.
According to the present invention, composition or concentrated solution preferably include at least one Synolac or modified alkyd resin and/or dry vegetable oil as organic chemistry tackiness agent.According to the present invention, preferably use oil-contg higher than 45 % by weight, preferably the Synolac of 50 to 68 % by weight.
All or part of be fixed agent of above-mentioned tackiness agent (mixture) or softening agent (mixture) replace.Described additive is intended to prevent active compound volatilization, and crystallization or precipitation.Described additive preferably replaces 0.01 to 30% tackiness agent (tackiness agent using based on 100%).
Softening agent comes from following chemical classes: phthalic ester, for example dibutyl phthalate, dioctyl phthalate (DOP) or benzyl butyl phthalate, phosphoric acid ester, for example tributyl phosphate, adipic acid ester, oneself two (2-ethylhexyl) acid esters for example, stearate, for example butyl stearate or amyl stearate, oleic acid ester, for example butyl oleate, glycerol ether or relatively glycol ether, glycerine ester and the p-toluenesulfonic esters of high molecular.
Fixing agent is chemically based on polyethylene alkyl ether, for example polyvinyl methyl ethermaleic anhydride, or ketone, for example benzophenone and ethylene benzophenone.
The water that also has that is especially suitable for use as solvent or thinner, if suitable, can be used as the mixture with one or more above-mentioned organic chemistry solvents or thinner, emulsifying agent and dispersion agent.
Especially effectively wood protection completes by large-scale mill retting technique, for example vacuum, two vacuum or pressure process.
If suitable, use the composition of (ready-to-use) also can comprise in addition other insecticides, and if suitable one or more mycocides in addition.
The blendable annexing ingredient being applicable to is preferably insecticide and the mycocide proposing in WO 94,/29 268.The compound proposing in this document is the application's a part clearly.
Most preferred blendable component has: insecticide, for example Chlorpyrifos 94, phoxim, deinsectization silicon ether (silafluofin), nail body Cypermethrin, cyfloxylate, Cypermethrin, Deltamethrin, permethrin (permethrin), imidacloprid, NI-25, flufenoxuron, HEXAFLUMURON, transfluthrin, thiacloprid, methoxyphenoxid and desinsection is grand, clothianidin (chlothianidin), spinosad, tefluthrin;
And mycocide, for example oxole bacterium (epoxyconazole), own azoles alcohol, penta encircle azoles, Wocosin 50TK, tebuconazole, cyproconazole, ring penta azoles bacterium, IMAZALIL (imazalil), Pecudin, tolylfluanid, the iodo-2-propynyl butyl carbamate of 3-, N-octyl group isothiazoline-3-ketone and the chloro-N-octyl group isothiazoline-3-of 4,5-bis-ketone.
Compound of the present invention can, simultaneously for the protection of the object, particularly hull, sieve, net, building, mooring and the signalling system that contact with salt water or brackish water, prevent that it from producing dirt.
Oligochaeta (Oligochaeta) animal by anchorage, Serpulidae (Serpulidae) for example, with the kind by shell (shell) and Ledamorpha class (goose tender tea leaves lotus (goose barnacles)), for example various tender tea leaves lotuses belong to (Lepas) and armour tender tea leaves lotus belongs to (Scalpellum) kind, or by the kind of barnacle (Balanomorpha) class (barnacle (acorn barnacles)), for example Balanus (Balanus) or tortoise foot belong to the dirt that (Pollicipes) kind causes, can increase the friction resistance of ship, thereby cause the remarkable increase by higher energy expenditure and the operating cost that extra frequent stop produces on graving dry dock.
Except algae, for example, outside the dirt that Ectocarpus (Ectocarpus sp.) and Ceratium (Ceramium sp.) cause, the dirt being caused by the Entomostraka class that is included into the anchorage that is generically and collectively referred to as cirrus guiding principle (Cirripedia) (cirriped crustaceans) is particularly important also.
Surprisingly, when having now found that compound of the present invention separately or combining with other active compounds, there is outstanding antifouling activity.
Separately or be combined with compound of the present invention with other active compounds, can avoid using heavy metal in following compound, for example, at two (trialkyltin) sulfide, lauric acid tri-n-butyl tin, tri-n-butyltin chloride, Red copper oxide (I), ethyl tin monochloride, three normal-butyls (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenumdisulphide, weisspiessglanz, n-butyl titanate polymer, phenyl (two pyridine) Trichlorobismuthine, tri-n-butyl tin fluoride, ethylenebis thiocarbamate manganese (manganese ethylenebisthiocarbamate), ziram, ethylenebis zinc thiocarbamate, zinc salt and the mantoquita of 2-pyridine thiol 1-oxide compound (2-pyridinethiol 1-oxide), two Methyl disulfide are for the ethylenebis thiocarbamate (bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate) of carbamyl zinc, zinc oxide, ethylenebis dithiocarbamic acid cuprous (copper (I) ethylene-bisdithiocarbamate), cupric thiocyanide, in copper naphthenate and tributyltin halogenide, or significantly reduce the concentration of described compound.
If suitable, the antifouling varnish of use also can comprise other active compounds in addition, preferred algicide, mycocide, weedicide, invertebrate poison, or other antifouling activity compounds.
The component of being combined with antifouling composition of the present invention being preferably applicable to has:
Algicide, for example
2-tertiary butyl amino-4-cyclopropylamino-6-methyl sulfo--1,3,5-triazine, dichlorophen, Diuron Tech (diuron), endothal (endothal), fentinacetate (fentinacetate), isoproturon (isoproturon), methabenzthiazuron (methabenzthiazuron), Oxyfluorfen (oxyfluorfen), quinoclamine (quinoclamine) and terbutryn (terbutryne);
Mycocide, for example
Benzo [b] thiophene carboxylic acid cyclohexyl amide S, S-dioxide, Pecudin, the iodo-2-propynyl ester of fluorfolpet, butyl carboxylamine 3-, tolylfluanid and pyrroles, for example
Penta ring azoles, cyproconazole, oxole bacterium, own azoles alcohol, ring penta azoles bacterium, Wocosin 50TK and tebuconazole;
Invertebrate poison, for example
Fentinacetate, Halizan, metmercapturon, niclosamide, UC-51762 and trimethacarb; Iron chelate (Fe chelate);
Or conventional antifouling activity compound, for example
4, the chloro-2-octyl group-4-of 5-bis-isothiazoline-3-ketone, diiodomethylparatryl sulfone, 2-(N, N-dimethyl thiocarbamoyl sulphur)-5-nitrothiazole base (2-(N, N-dimethylthiocarbamoylthio)-5-nitrothiazyl), the sylvite of 2-pyridine thiol 1-oxide compound, mantoquita, sodium salt and zinc salt, pyridine-triphenyl borane, the tetrabutyl two tin oxyethane, 2, 3, 5, 6-tetrachloro-4-(methylsulfonyl) pyridine, 2, 4, 5, 6-tetrachloro isophthalonitrile, tetramethyl-thiuram disulfide and 2, 4, 6-trichlorophenyl maleimide.
The antifouling composition using comprises 0.001 to 50 % by weight, the particularly active compound of the present invention of 0.01 to 20 % by weight concentration.
And antifouling composition of the present invention also comprises conventional component, Ungerer for example, Chem.Ind.1985,37,730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, the component described in 1973.
Except of the present inventionly killing algae, fungicidal, killing mollusk active compound and kill insect active compound, antifouling varnish also comprises, particularly tackiness agent.
The example of generally acknowledging tackiness agent has: the polyvinyl chloride in solvent system, chlorinated rubber in solvent system, acrylic resin in solvent system, particularly aqueous systems, vinylchlorid/vinyl acetate copolymer system of water dispersion form or organic solvent system form, Butadiene/Styrene/acrylic-nitrile rubber, siccative oil, for example Toenol 1140, resin ester or the modification hardening resin of being combined with tar or pitch, pitch and epoxy compounds, a small amount of chlorine rubber (chlorine rubber), Chlorinated Polypropylene III and ethenoid resin.
If suitable, paint also comprises mineral dye, pigment dyestuff or the tinting material that is preferably insoluble to salt water.Paint can further comprise the material that makes active compound controlled release, for example rosin.And paint also can comprise softening agent, affect properties-correcting agent and other conventional ingredients of rheological properties.Compound of the present invention or said mixture also can be contained in polishing antifouling system.
Active compound is also suitable for preventing and treating animal pest, particularly insect, arachnid and the acarid of finding in enclosed space, described enclosed space such as residence, factory floor, office, vehicles workplace (vehicle hall) etc.Described compound can separately or be combined with other active compounds and auxiliary agent and be killed insect product for preventing and treating the family expenses of described insect.Described compound is to sensitive species and resistance species and all the etap all has activity.Described insect comprises:
Scorpionida (Scorpionidea), for example, the yellow scorpion (Buthus occitanus) in Mediterranean Sea.
Acarina (Acarina), for example, adobe tick (Argas persicus), argas reflexus (Argas reflexus), tongue mite subspecies (Bryobia ssp.), Dermanyssus gallinae (Dermanyssus gallinae), sweet mite (Glyciphagus domesticus) is had a liking for by family, tampan tick (Ornithodorus moubat), brown dog tick (Rhipicephalus sanguineus), eutrombicula alfreddugesi (Trombicula alfreddugesi), Neutrombicula autumnalis, spy has a liking for skin mite (Dermatophagoides pteronissimus), method is had a liking for skin mite (Dermatophagoides forinae).
Araneida (Araneae), for example, catching bird spider (Aviculariidae), circle spider (Araneidae).
Opiliones (Opiliones), for example, chelifer (Pseudoscorpiones chelifer), the blind spider of the Chang Shin of Pseudoscorpiones cheiridium, (Opiliones phalangium).
Isopoda, for example, comb beach louse, ball pillworm.
Sufficient order doubly, for example, Blaniulus guttulatus, mountain cricket worm (Polydesmus spp.).
Lip foot order, for example, DIWUGONG (Geophilus spp.).
Silverfish order (Zygentoma), for example, comb silverfish belongs to (Ctenolepisma spp.), silverfish, robber fireworm (Lepismodes inquilinus).
Blattodea, for example, oriental cockroach, blatta germanica, Asia Lian (Blattella asahinai), leucophaea maderae, angle abdomen Lian belong to (Panchlora spp.), wooden Lian belongs to (Parcoblatta spp.), Australian cockroach (Periplaneta australasiae), periplaneta americana, large brown large Lian (Periplaneta brunnea), smoke Perilpaneta americana (Periplaneta fuliginosa), brown belt blattaria (Supella longipalpa).
Saltatoria (Saltatoria), for example, the Xi of family.
Dermaptera, for example, European earwig.
Isoptera, for example, kalotermitid belongs to (Kalotermes spp.), Reticulitermes.
Corrodentia (Psocoptera), for example, Lepinatus spp., powder corrodent belong to (Liposcelis spp.).
Coleoptera, for example, Anthrenus, the moth-eaten genus of fur, khapra beetle genus, a long ostomatid (Latheticus oryzae), hidden instep cuckoo Eimeria (Necrobia spp.), Ptinus, lesser grain borer, grain weevil (Sitophilus granarius), rice weevil (Sitophilus oryzae), sitophilus zea-mais (Sitophilus zeamais), Stegobium paniceum (Stegobium paniceum).
Diptera, for example, Aedes aegypti (Aedes aegypti), Aedes albopictus (Aedes albopictus), aedes taeniorhynchus (Aedes taeniorhynchus), Anopheles, calliphora erythrocephala, great number fiber crops horsefly (Chrysozona pluvialis), five band culex pipiens pollens (Culex quinquefasciatus), northern house (Culexpipiens), ring beak culex (Culex tarsalis), Drosophila (Drosophila spp.), Fannia canicularis (Fannia canicularis), housefly (Musca domestica), owl midge, Sarcophaga carnaria, Simulium, tatukira (Stomoxys calcitrans), Europe daddy-longlegs.
Lepidopteran, for example, lesser wax-moth (Achroia grisella), greater wax moth, Indian meal moth (Plodia interpunctella), stopper rain moth (Tinea cloacella), bag rain moth, curtain rain moth.
Siphonaptera, for example, ctenocephalides canis (Ctenocephalides canis), ctenocephalides felis (Ctenocephalides felis), Pulex irritans (Pulex irritans), chigo (Tunga penetrans), Xanthopsyllacheopis.
Hymenoptera, for example, blazon hunchbacked ant (Camponotus herculeanus), black smelly ant (Lasius fuliginosus), black ant (Lasius niger), Lasius umbratus, MonomoriumMayr, Paravespula spp., Pavement Ant (Tetramorium caespitum).
Anoplura (Anoplura), for example, head louse (Pediculus humanus capitis), body louse, crab louse (Phthirus pubis).
Heteroptera, for example, cimex hemipterus (Cimex hemipterus), bed bug, phodnius prolixus, invasion triatomid (Triatoma infestans).
Described active compound can be separately or the active compound applicable with other, for example phosphoric acid ester, carbamate, pyrethroid, anabasine (neonicotinoid), growth regulator or combine for family expenses insecticide field from the active compound of other known insecticide kinds.
Described compound is used for following product: aerosol, vacuum spraying (pressure-free spray) product, for example pump and atomizer (atomizer) spraying, automatic atomizing system, aerosol producer, foam, gel, the vaporizer product with the vaporizer tablet (evaporator tablet) that Mierocrystalline cellulose or polymkeric substance make, liquid evaporator, gel and thin-film evaporator, the vaporizer that propelling agent promotes, unpowered (energe-free) or passive (passive) vapo(u)rization system, catch moth paper, catch moth bag and catch moth glue, as granule or powder agent, for the bait shed or for Poison bait station (bait station).
Active compound of the present invention also can be used as defoliating agent, siccative, removes cauline leaf agent (haulm killer), and the agent of particularly cutting weeds.Broadest being interpreted as all plants that do not need its place growth of implication of weeds.Material of the present invention, as non-selective or selective herbicide, depends primarily on rate of application.
Active compound of the present invention can be used for, for example following plant:
broadleaf weed with subordinate:hemp belongs to (Abutilon), Amaranthus (Amaranthus), Ambrosia (Ambrosia), Anoda, Anthemis (Anthemis), Aphanes, atriplex (Atriplex), daisy belongs to (Bellis), Bidens bipinnata belongs to (Bidens), shepherd's purse belongs to (Capsella), bristlethistle (Carduus), Cassia (Cassia), bachelor's-button (Centaurea), Chenopodium (Chenopodium), Cirsium (Cirsium), japanese bearbind belongs to (Convolvulus), Datura (Datura), beggar-ticks (Desmodium), thorn Rumex (Emex), Erysimum (Erysimum), Euphorbia (Euphorbia), weasel hemp nettle belongs to (Galeopsis), ox achyranthes chrysanthemum spp (Galinsoga), galium (Galium), lotus belongs to (Hibiscus), Ipomoea (Ipomoea), Kochia (Kochia), lamium (Lamium), separate row Vegetable spp (Lepidium), Vandellia (Lindernia), Matricaria (Matricaria), Mentha (Mentha), mercury belongs to (Mercurialis), Mullugo, Myosotis sylvatica belongs to (Myosotis), papaver (Papaver), ipomoea (Pharbitis), Plantago (Plantago), Polygonum (Polygonum), Portulaca (Portulaca), Ranunculus (Ranunculus), Rhaphanus (Raphanus), Han Lepidium (Rorippa), joint joint Lepidium (Rotala), Rumex (Rumex), Salsola (Salsola), Senecio (Senecio), Daubentonia (Sesbania), chrysanthemum harvest spp (Sida), sinapsis alba belongs to (Sinapis), Solanum (Solanum), sonchus L (Sonchus), cusp Pittosporum (Sphenoclea), Stellaria (Stellaria), Dandelion (Taraxacum), herba thlaspis genus (Thlaspi), Clover (Trifolium), Urtica (Urtica), Veronica (Veronica), Viola (Viola), Xanthium (Xanthium).
dicotyledonous crops with subordinate:arachis (Arachis), Beta (Beta), Btassica (Brassica), Cucumis (Cucumis), Cucurbita (Cucurbita), Helianthus (Helianthus), Daucus (Daucus), Glycine (Glycine), Gossypium (Gossypium), Ipomoea (Ipomoea), Lactuca (Lactuca), linum (Linum), tomato belongs to (Lycopersicon), Nicotiana (Nicotiana), Phaseolus (Phaseolus), Pisum (Pisum), Solanum (Solanum), Vicia (Vicia).
monocotyledon weed with subordinate:aegilops (Aegilops), Agropyron (Agropyron), Agrostis (Agrostis), amur foxtail belongs to (Alopecurus), Apera, Avena (Avena), Brachiaria (Brachiaria), Brome (Bromus), Cenchrus (Cenchrus), Commelina (Commelina), Cynodon (Cynodon), Cyperus (Cyperus), talon eria (Dactyloctenium), knotgrass (Digitaria), Echinochloa (Echinochloa), Eleocharis (Eleocharis), yard grass belongs to (Eleusine), Eragrostis (Eragrostis), wild Panicum (Eriochloa), festuca (Festuca), genus fimbristylis (Fimbristylis), Heteranthera (Heteranthera), cogon (Imperata), ischaemum (Ischaemum), Sprangletop (Leptochloa), lolium (Lolium), Monochoria (Monochoria), Panicum (Panicum), Paspalum (Paspalum), phalaris arundinacea (Phalaris), ladder forage spp (Phleum), Poa L. (Poa), Rottboellia exaltata L. F. belongs to (Rottboellia), Sagittaria (Sagittaria), Scirpus (Scirpus), setaria (Setaria), sorghum (Sorghum).
monocot crops with subordinate:allium (Allium), Ananas (Ananas), Asparagus (Asparagus), Avena (Avena), Hordeum (Hordeum), Oryza (Oryza), Panicum (Panicum), saccharum (Saccharum), Secale (Secale), sorghum (Sorghum), triticale belong to (Triticale), Triticum (Triticum), Zea (Zea).
Yet the use of active compound of the present invention never only limits to above-mentioned genus, but extend in an identical manner other plant.
According to concentration, active compound of the present invention be suitable for for example industrial belt and railway and have tree and without tree road and place in for non-selective controlling weeds.Equally, active compound of the present invention also can be used for preventing and treating the weeds in perennial crop, and the weeds in selectivity control annual crop; Wherein the example of perennial crop has: forest, ornamental trees are planted, fruit tree, vineyard, citrus woods, nut woods, banana plantation, cafetal, tea plantation, rubber plantation, oil palm plantation, cocoa plantation, soft fruit (soft fruit) is planted and hop field (hop field), meadow, lawn and grassland.
Formula of the present invention (I) compound, when for soil and ground plant parts, has very strong weeding activity and very wide action spectrum.In a way, described compound is also applicable to unifacial leaf and the broadleaf weed in selectivity control unifacial leaf and dicotyledonous crops, before emerging He after emerging, all can.
Active compound of the present invention also can finite concentration or rate of application be used for preventing and treating animal pest and fungi or bacterial plant disease.If suitable, described compound also can be used as intermediate or the precursor of synthetic other active compounds.
Active compound can be converted into conventional formulation, for example solution, emulsion, wettable powder, suspension agent, pulvis, powder agent, paste, soluble powder, granule, outstanding newborn enriching agent, with the meticulous capsule in active compound impregnated natural and synthetics and polymkeric substance.
Described preparation is prepared in a known way, for example, active compound is mixed with weighting agent, mixes with liquid solvent and/or solid carrier, simultaneously alternative tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or the whipping agent of using.
If the weighting agent using is water, also can use, for example organic solvent is as solubility promoter.Applicable liquid solvent mainly contains: aromatics, for example dimethylbenzene, toluene or alkylnaphthalene; Chlorination aromatics and chlorinated aliphatic, for example chlorobenzene, vinylchlorid or methylene dichloride; Aliphatic hydrocarbon, for example hexanaphthene or paraffin, as petroleum fractions, mineral oil and vegetables oil; Alcohol, for example butanols or ethylene glycol and ether thereof and ester; Ketone, for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Intensive polar solvent, for example dimethyl formamide and dimethyl sulfoxide (DMSO), and water.
Applicable solid carrier has: the natural mineral of ammonium salt and pulverizing for example, for example kaolin, clay, talcum powder, chalk, quartz, attapulgite, montmorillonite or diatomite, and the synthetic mineral of pulverizing, for example silicon-dioxide of porphyrize, aluminum oxide and silicate; The solid carrier that is suitable for granule has: for example pulverize and the natural rock of classification for example calcite, marble, float stone, sepiolite and rhombspar, and synthetic inorganic and organic powder particles, and organic materials particle for example wood sawdust, coconut husk, corn cob and tobacco stem; Applicable emulsifying agent and/or whipping agent have: for example nonionic and anionic emulsifier, for example polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and protein hydrolyzate; Applicable dispersion agent has: for example lignin sulfite waste lye and methylcellulose gum.
In preparation, can use tackifier, the natural and synthetic polymer of carboxymethyl cellulose and powder, particle or latex shape for example, for example Sudan Gum-arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, for example kephalin and Yelkin TTS, and synthetic phospholipid.Other additives can be mineral oil and vegetables oil.
Can use tinting material, for example mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye, for example alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff, and micro-nutrients for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Preparation generally comprises 0.1 to 95 % by weight, the preferred active compound of 0.5 to 90 % by weight.
The form that active compound of the present invention can itself or its preparation and known weedicide and/or the material (" safener ") that improves farm crop tolerance are mixed for control of weeds object, can mix in advance or in-tank mixing (tank mix).Also can with the weedicide Product mix that contains one or more known weedicides and safener.
The weedicide that is suitable for mixing is known weedicide, for example:
Acetochlor (acetochlor), acifluorfen (acifluorfen (sodium)), aclonifen (aclonifen), alachlor (alachlor), alloxydim (alloxydim (sodium)), ametryn (ametryne), amicarbazone (amicarbazone), first alachlor (amidochlor), amidosulfuron (amidosulfuron), anilofos (anilofos), sulphur grass spirit (asulam), atrazine (atrazine), azafenidin (azafenidin), azimsulfuron (azimsulfuron), beflubutamid (beflubutamid), benazolin (benazolin (ethyl)), benfuresate (benfuresate), benbbensulfuronmethyl (bensulfuron (methyl)), bentazone (bentazone), benzfendizone (benzfendizone), benzobicylon (benzobicyclon), benzofenap (benzofenap), benzoylpropethyl (benzoylprop (ethyl)), bialaphos (bialaphos), bifenox (bifenox), two careless ether (bispyribac (sodium)), bromobutide (bromobutide), bromine phenol dirty (bromofenoxim), bromoxynil (bromoxynil), Butachlor technical 92 (butachlor), butafenacil (butafenacil (allyl)), butroxydim (butroxydim), butylate (butylate), cafenstrole (cafenstrole), quinone oximes grass (caloxydim), carbetamide (carbetamide), carfentrazone (carfentrazone (ethyl)), chlomethoxyfen (chlomethoxyfen), chloramben (chloramben), chloridazon (chloridazon), chlorimuronethyl (chlorimuron (ethyl)), chlornitrofen (chlornitrofen), chlorine sulphur grand (chlorsulfuron), chlorotoluron (chlortoluron), cinidon-ethyl (cinidon (ethyl)), cinmethylin (cinmethylin), cinosulfuron (cinosulfuron), clefoxidim (clefoxydim), clethodim (clethodim), alkynes oxalic acid (clodinafop (propargyl)), clomazone (clomazone), clomeprop (clomeprop), clopyralid (clopyralid), clopyrasulfuron (methyl), cloransulammethyl (cloransulam (methyl)), cumyluron, cyanazine (cyanazine), cybutryne, cycloate (cycloate), AC322140 (cyclosulfamuron), cycloxydim (cycloxydim), cyhalofop-butyl (cyhalofop (butyl)), 2,4-D, 2,4-DB, desmedipham (desmedipham), di_allate (diallate), dicamba 98, essence 2,4-drips propionic acid (dichlorprop (P)), diclofop-methyl (diclofop (methyl)), diclosulam (diclosulam), acetyl alachlor (diethatyl (ethyl)), difenzoquat (difenzoquat), diflufenican (diflufenican), diflufenzopyr (diflufenzopyr), dimefuron (dimefuron), dimepiperate, dimethachlor (dimethachlor), dimethametryn (dimethametryn), dimethenamid (dimethenamid), dimexyflam, dinitramine (dinitramine), diphenamide (diphenamid), diquat (diquat), dithiopyr (dithiopyr), Diuron Tech (diuron), daimuron, epropodan, EPTC, esprocarb (esprocarb), ethalfluralin (ethalfluralin), ethametsulfuron (ethametsulfuron (methyl)), ethofumesate (ethofumesate), HC252 (ethoxyfen), ethoxysulfuron (ethoxysulfuron), ethobenzanid (etobenzanid), fenoxapropPethyl (fenoxaprop (P-ethyl)), fentrazamide (fentrazamide), wheat straw fluorine (isopropyl ester, isopropyl ester-L, methyl esters) (flamprop (isopropyl ,-isopropyl-L ,-methyl)), flazasulfuron (flazasulfuron), florasulam (florasulam), efficient fluazifop (fluazifop (P-butyl)), fluazolate (fluazolate), flucarbazonesodium (flucarbazone (sodium)), flufenacet (flufenacet), flumetsulam (flumetsulam), methylarsonic acid (flumiclorac (pentyl)), flumioxazin (flumioxazin), flumipropyn, flumetsulam (flumetsulam), fluometuron (fluometuron), fluorochloridone (fluorochloridone), fluoroglycofenethyl (fluoroglycofen (ethyl)), flupoxam (flupoxam), flupropacil, flurpyrsulfuron (methyl ,-sodium), flurenol (flurenol (butyl)), fluridone (fluridone), fluroxypyr (butoxy propyl group ,-meptyl) (fluroxypyr (butoxypropyl ,-meptyl)), flurprimidol (flurprimidol), flurtamone (flurtamone), fluthiacetmethyl (fluthiacet (methyl)), fluthiamide, fomesafen (fomesafen), formyl ammonia sulphur grand (foramsulfuron), grass ammonium phosphine (glufosinate (ammonium)), glyphosate isopropyl amine salt (glyphosate (isopropylammonium), fluorine nitre sulphonamide (halosafen), fluazifop-butyl (haloxyfop, haloxyfopPmethyl) (haloxyfop (ethoxyethyl ,-P-methyl)), hexazinone (hexazinone), miaow oxalic acid (imazamethabenz (methyl)), imazamethapyr, imazamox (imazamox), imazapic, imazapyr (imazapyr), imazaquin (imazaquin), imazethapyr (imazethapyr), imazosulfuron (imazosulfuron), iodosulfuron methyl sodium (iodosulfuron (methyl ,-sodium)), ioxynil (ioxynil), isopropalin (isopropalin), isoproturon (isoproturon), isouron (isouron), ixoxaben (isoxaben), isoxachlorotole (isoxachlortole), isoxaflutole (isoxaflutole), isoxapyrifop (isoxapyrifop), lactofen (lactofen), lenacil (lenacil), methoxydiuron (linuron), MCPA, Vi par, mefenacet (mefenacet), mesotrione (mesotrione), metamitron (metamitron), metazachlor (metazachlor), methabenzthiazuron (methabenzthiazuron), metobenzuron (metobenzuron), metobromuron (metobromuron), α-metolachlor ((alpha-) metolachlor), metosulam (metosulam), metoxuron (metoxuron), piperazine humulone (metribuzin), metsulfuronmethyl (metsulfuron (methyl)), molinate (molinate), monolinuron (monolinuron), naproanilide (naproanilide), napropamide (napropamide), neburon (neburon), nicosulfuron (nicosulfuron), norflurazon (norflurazon), orbencarb (orbencarb), oryzalin (oryzalin), oxadiargyl (oxadiargyl), oxadiazon (oxadiazon), oxasulfuron (oxasulfuron), oxaziclomefone (oxaziclomefone), oxyfluorfen (oxyfluorfen), Paraquat (paraquat), n-nonanoic acid (pelargonic acid), pendimethalin (pendimethalin), pendralin, pentoxazone (pentoxazone), phenmedipham (phenmedipham), fluorine pyrrole acyl grass amine (picolinafen), piperophos (piperophos), the third careless amine (pretilachlor), primisulfuronmethyl (primisulfuron (methyl)), profluazol (profluazol), prometryn (prometryn), propachlor (propachlor), Stam F-34 (propanil), propaquizafop (propaquizafop), propisochlor (propisochlor), propoxycarbazone (sodium), propyzamide (propyzamide), prosulfocarb (prosulfocarb), prosulfuron (prosulfuron), pyrrole grass ether (pyraflufen (ethyl)), pyraclonil (pyrazogyl), pyrazolate (pyrazolate), pyrazosulfuronmethyl (pyrazosulfuron (ethyl)), pyrazoxyfen (pyrazoxyfen), pyribenzoxim (pyribenzoxim), pyributicarb (pyributicarb), pyridate (pyridate), pyridatol, pyriftalid (pyriftalide), KIH 6127 (pyriminobac (methyl)), pyrithiobacsodium (pyrithiobac (sodium)), quinclorac (quinchlorac), quinmerac (quinmerac), quinoclamine (quinoclamine), quizalofop (quizalofopPethyl, quinoline standing grain sugar ester) (quizalofop (P-ethyl ,-P-tefuryl)), rimsulfuron (rimsulfuron), sethoxydim (sethoxydim), simazine (simazine), simetryn (simetryn), sulphur humulone (sulcotrione), sulfentrazone (sulfentrazone), sulfometuronmethyl (sulfometuron (methyl)), glyphosate (sulfosate), sulfosulfuron (sulfosulfuron), tebutam (tebutam), tebuthiuron (tebuthiuron), tepraloxydim, terbuthylazine (terbuthylazine), terbutryn (terbutryn), P DimethenamidP (thenylchlor), thiafluamide, thrizopyr (thiazopyr), thiadiazoles grass amine (thidiazimin), thifensulfuronmethyl (thifensulfuron (methyl)), thiobencarb (thiobencarb), tiocarbazil (tiocarbazil), tralkoxydim (tralkoxydim), triallate (triallate), triasulfuron (triasulfuron), tribenuron-methyl (tribenuron (methyl)), trichlopyr (triclopyr), tridiphane (tridiphane), trifluralin (trifluralin), trifloxysulfuron (trifloxysulfuron), triflusulfuronmethyl (triflusulfuron (methyl)), tritosulfuron (tritosulfuron).
Be suitable for the known safener that also has mixing, for example:
AD-67, BAS-145138, benoxacor, cloquitocet_mexyl, cyometrinil, 2,4-D, DKA-24, dichlormide, daimuron, fenclorim, fenchlorazole-ethyl, solution grass amine, fluxofenim, Xie Cao oxazole, isoxadifen-ethyl, MCPA, mecopropP (mecoprop (P)), mefenpyrdiethyl, MG-191, oxabetrinil, PPG-1292, R-29148.
Also can with other known activity compound, for example mycocide, insecticide, acarus-killing, nematocides, bird repellent, nutrient for plants and soil conditioner.
Active compound can itself, its dosage form or type of service prepared therefrom use by further dilution, for example i.e. solution of use, suspension agent, emulsion, pulvis, paste and granule.They are used in a usual manner, for example, sprinkle to water, spraying, atomization (atomizing), shed (spreading).
Active compound of the present invention both can be before plant have emerged, also can go out postemergence application plant.Also can before plantation, be sneaked in soil.
The rate of application of active compound can change in the scope of non-constant width.Substantially the character that depends on required drug effect.Generally speaking, rate of application is the active compound of per hectare land area 1g to 10kg, preferably per hectare 5g to 5kg.
Material of the present invention has microbiocidal activity, can be in Crop protection and material protection for example, for preventing and treating undesired microorganism, fungus and bacterium.
Mycocide can be for preventing and treating plasmodiophora brassicae (Plasmodiophoromycetes), oomycetes (Oomycetes), chytrid (Chytridiomycetes), zygomycetes (Zygomycetes), ascomycetes (Ascomycetes), basidiomycetes (Basidiomycetes) and imperfect fungi (Deuteromycetes) in Crop protection.
Bactericide can be for preventing and treating pseudomonas (Pseudomonadaceae), root nodule bacterium (Rhizobiaceae), enterobacteria (Enterobacteriaceae), coryneform bacteria (Corynebacteriaceae) and streptomycete (Streptomycetaceae) in Crop protection.
Some pathogenic agent that cause fungus and bacterium disease that are included into above-mentioned general name can be used as limiting examples proposition:
Yellow unit cell (Xanthomonas) bacterial classification, for example, the mutation (Xanthomonas campestris pv.oryzae) of causing a disease of xanthomonas campestris paddy rice;
False unit cell (Pseudomonas) bacterial classification, for example, the mutation (Pseudomonas syringae pv.lachrymans) of causing a disease of pseudomonas syringae cucumber;
Ou Wenshi (Erwinia) bacterial classification, for example, separates starch Erwinia (Erwinia amylovora);
Rotten mould (Pythium) bacterial classification, for example, Pythium ultimum (Pythium ultimum);
Epidemic disease mould (Phytophthora) bacterial classification, for example, phytophthora infestans (Phytophthora infestans);
False downy mildew (Pseudoperonospora) bacterial classification, for example, the false downy mildew (Pseudoperonospora cubensis) of careless false downy mildew (Pseudoperonospora humuli) or Cuba;
Axle downy mildew (Plasmopara) bacterial classification, for example, the raw axle downy mildew (Plasmopara viticola) of grape;
Dish downy mildew (Bremia) bacterial classification, for example, lettuce dish downy mildew (Bremia lactucae);
Downy mildew (Peronospora) bacterial classification, for example, pea downy mildew (Peronospora pisi) or Cruciferae downy mildew (P.brassicae);
Powdery mildew (Erysiphe) bacterial classification, for example, Erysiphe graminis (Erysiphe graminis);
Sphaerotheca (Sphaerotheca) bacterial classification, for example, Flower of Garden Balsam list softgel shell (Sphaerotheca fuliginea);
Podosphaera (Podosphaera) bacterial classification, for example, white cross hair list softgel shell (Podosphaera leucotr icha);
Venturia (Venturia) bacterial classification, for example, apple black star bacteria (Venturia inaequalis);
Nuclear cavity Pseudomonas (Pyrenophora) bacterial classification, for example, circle nuclear cavity bacteria (Pyrenophorateres) or wheat class nuclear cavity bacteria (P.graminea) (conidial form: Drechs lera, syn:Helminthosporium);
Cochliobolus belongs to (Cochliobolus) bacterial classification, for example, and standing grain cochliobolus (Cochliobolus sativus) (conidial form: Drechslera, syn:Helminthosporium);
Uromyces (Uromyces) bacterial classification, for example, wart top uromyce (Uromyces appendiculatus);
Handle rest fungus (Puccinia) bacterial classification, for example, Puccinia recondita (Puccinia recondita);
Sclerotinia (Sclerotinia) bacterial classification, for example, sclerotinite (Sclerotinia sclerotiorum);
Tilletia (Tilletia) bacterial classification, for example, Tilletia caries (Tilletia caries);
Ustilago (Ustilago) bacterial classification, for example, naked smut (Ustilago nuda) or oat ustilago (Ustilago avenae);
Film lead fungi belongs to (Pellicularia) bacterial classification, for example, and assistant assistant wooden film lead fungi (Pellicularia sasakii);
Pears spore (Pyricularia) bacterial classification, for example, Magnaporthe grisea (Pyricularia oryzae);
Fusarium (Fusarium) bacterial classification, for example, yellow sickle spore (Fusarium culmorum);
Staphlosporonites (Botrytis) bacterial classification, for example, Botrytis cinerea (Botrytis cinerea);
Septoria (Septoria) bacterial classification, for example, clever withered septoria musiva (Septoria nodorum);
Leptosphaeria (Leptosphaeria) bacterial classification, for example, Leptosphaeria nodorum;
Cercospora (Cercospora) bacterial classification, for example, turns grey tail spore (Cercospora canescens);
Alternaria (Alternaria) bacterial classification, for example, rape chain lattice spore (Alternaria brassicae); With
False Cercosporalla (Pseudocercosporella) bacterial classification, for example, wheat-based maize ear rot bacterium (Pseudocercosporella herpotrichoides).
Active compound of the present invention also has extraordinary strengthening effect (fortifying action) in plant.Therefore they can be used for transferring the defence capability of plant to the invasion and attack of undesired microorganism.
In the present invention, the implication of plant strengthening (induction of resistance) material is interpreted as exciting the material of plant defense system, this material makes treated plant when inoculating undesired microorganism subsequently, can show the stronger resistance to described microorganism.
In this case, the implication of undesired microorganism is interpreted as phytopathogenic fungi, bacterium and virus.Therefore, material of the present invention can be used for protective plant is avoided above-mentioned pathogenic agent invasion and attack in the certain period after processing.With active compound, process after plant, the protection period providing can extend to more than 1 to 10 day conventionally, preferably 1 to 7 day.
The good plant tolerance that active compound has under control plant disease desired concn, makes to process the position, ground of plant, in-vitro propagate strain (propagation stock) and seed and soil.
Active compound of the present invention is also applicable to improve crop yield.In addition, they also show the toxicity of reduction and good plant tolerance.
Under finite concentration or rate of application, compound of the present invention, goes back useful as herbicides if suitable, for affecting plant-growth and control animal pest.If suitable, they also can be used as intermediate or the precursor of synthetic other active compounds.
Aspect material protection, compound of the present invention can be used for safeguard industries material and avoids infecting of undesired microorganism and destroy.
In the present invention, the implication of Industrial materials is interpreted as making to be prepared for industrial non-living body (non-living) material.For example, intend avoiding that microorganism changes (change) or the Industrial materials that destroy can be tackiness agent, sizing material, paper and sheet material, fabric, leather, timber, paint and plastics, cooling lubricant (cooling lubricant) and other can be subject to the material of microbial infection or destruction by active compound protection of the present invention.Production plant's parts that can be damaged by microbial reproduction, for example chilled(cooling) water return (CWR) also can be mentioned in the scope of material to be protected.The Industrial materials that can mention are within the scope of the present invention preferably tackiness agent, sizing material, paper and sheet material, leather, timber, paint, cooling lubricant and heat transfer liquids, particularly preferably timber.
Can mention Industrial materials are degenerated (degrading) or the microorganism that changes is, for example bacterium, fungi, yeast, algae and mucus are biological.Active compound of the present invention preferably acts on fungi, particularly mould, timber fade fungi and wood-rotting fungi (basidiomycetes) and mucus biology and algae.
As an example following microorganism belonging to genus can be proposed:
Alternaria (Alternaria), for example, chain lattice spore (Alternaria tenuis),
Aspergillus (Aspergillus), for example, aspergillus niger (Aspergillus nigar),
Chaetomium (Chaetomium), for example, chaetomium globosum (Chaetomium globosum),
Coniophora, for example, Coniophora puetana,
Lentinus (Lentinus), for example, Lentinus tigrinus bacterium (Lentinus tigrinus),
Penicillium (Penicillium), for example, Penicillum glaucum (Penicillium glaucum),
Polyporus (Polyporus), for example, variegated pore fungus (Polyporus versicolor),
Aureobasidium genus (Aureobasidium), for example, Aureobasidium pullulans (Aureobasidium pullulans),
Core stem point belongs to (Sclerophoma), for example, and Sclerophoma pityophila,
Trichoderma (Trichoderma), for example, viride (Trichoderma viride),
Escherichia (Escherichia), for example, colon bacillus (Escherichia coli),
Rhodopseudomonas (Pseudomonas), for example, Pseudomonas aeruginosa (Pseudomonas aeruginosa), and
Staphylococcus (Staphylococcus), for example, streptococcus aureus (Staphylococcus aureus).
According to its specific physics and/or chemical property, active compound can be converted into conventional formulation, and for example the microcapsule in solution, emulsion, suspension agent, pulvis, foam, paste, granule, aerosol and polymkeric substance and seed pelleting (coating) composition and ULV are cooling and the atomizing preparation of heating.
Described preparation is prepared in a known way, for example, active compound is mixed with weighting agent, mixes with liquid solvent, pressurized liquefied gas and/or solid carrier, simultaneously alternative tensio-active agent, i.e. emulsifying agent and/or dispersion agent and/or the whipping agent of using.If the weighting agent using is water, also can use, for example organic solvent is as solubility promoter.Applicable liquid solvent mainly contains: aromatics, for example dimethylbenzene, toluene or alkylnaphthalene, chlorination aromatics or chlorinated aliphatic, for example chlorobenzene, vinylchlorid or methylene dichloride, aliphatic hydrocarbon, for example hexanaphthene or paraffin, as petroleum fractions, alcohol, for example butanols or ethylene glycol and ether thereof and ester, ketone, for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, for example dimethyl formamide and dimethyl sulfoxide (DMSO), or water.It is the liquid of gaseous state that the implication of liquefied gas weighting agent or carrier is interpreted as under standard temperature and normal atmosphere, aerosol propellants for example, for example halohydrocarbon, or butane, propane, nitrogen and carbonic acid gas.Applicable solid carrier has: the natural mineral of for example pulverizing is kaolin, clay, talcum powder, chalk, quartz, attapulgite, montmorillonite or diatomite for example, and the synthetic mineral of pulverizing for example silicon-dioxide, aluminum oxide and the silicate of porphyrize.The solid carrier that is suitable for granule has: for example pulverize and the natural rock of classification for example calcite, marble, float stone, sepiolite and rhombspar, or synthetic inorganic and organic powder particles, and organic materials particle for example wood sawdust, coconut husk, corn cob and tobacco stem.Applicable emulsifying agent and/or whipping agent have: for example nonionic and anionic emulsifier, for example polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, for example alkylaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate or protein hydrolyzate.Applicable dispersion agent has: for example lignin sulfite waste lye and methylcellulose gum.
In preparation, can use tackifier, the natural and synthetic polymer of carboxymethyl cellulose and powder, particle or latex shape for example, for example Sudan Gum-arabic, polyvinyl alcohol and polyvinyl acetate, or natural phospholipid for example kephalin and Yelkin TTS and synthetic phospholipid.Other additives can be mineral oil and vegetables oil.
Can use tinting material, for example mineral dye, for example ferric oxide, titanium oxide and Prussian blue, and organic dye for example alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff, and micro-nutrients for example molysite, manganese salt, boron salt, mantoquita, cobalt salt, molybdenum salt and zinc salt.
Preparation generally comprises 0.1 to 95 % by weight, the preferred active compound of 0.5 to 90 % by weight.
Active compound of the present invention can itself or its preparation form mix use with known mycocide, bactericide, acarus-killing, nematocides or insecticide, for example to widen action spectrum or to prevent resistance.Obtain in many cases synergistic effect, the activity of mixture is greater than the activity of each single component.
The example of applicable blending ingredients is as follows:
Mycocide:
2-phenylphenol, oxine vitriol, acibenzolar-S-methyl, aldimorph, amidoflumet, the acid of ammonia propyl-phosphine, ammonia propyl-phosphine acid potassium, andoprim, anilazine, penta ring azoles, nitrile Azoxystrobin, M 9834, benodanil, F-1991, sec.-propyl-benthiavalicarb, benzyl olefin(e) acid, isobutyl-benzyl olefin(e) acid, bialaphos, Niagara 9044, biphenyl, Bitertanol, miewensu, bromuconazole, the phonetic bacterium spirit of sulphur, powder is also fixed, butylamine, poly-sulfurated lime, capsimycin, Difolatan, Vancide 89, derosal, carboxin, carpropamide, Karvon, chinomethionate, the pest of going out azoles, benzene imidazoles bacterium, chloroneb, m-tetrachlorophthalodinitrile, chlozolinate, clozylacon, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, cyprofuram, Dagger G, two ethoxy imidazoles prestige, Pecudin, dichlone, dichlorophen, diclocymet, diclomezine, dicloran, the mould prestige of second, Difenoconazole, fluorine mepanipyrim, Milcurb, dimethomorph, dimoxystrobin, alkene azoles alcohol, alkene azoles alcohol-M, dinocap, pentanoic, Dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, Hinosan, oxole bacterium, Han Lening, Milstem, Truban, azolactone bacterium, fenamidone, fenapanil, fenarimol, RH-7592, first furan is drunk aniline, fenhexamid, plant clothing ester, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, Karbam Black, fluazinam, flubenzimine, Fu Evil bacterium, fluorine biphenyl bacterium, flumorph, fluoromide, fluoxastrobin, Fluquinconazole, flurprimidol, fluzilazol, flusulfamide, fultolanil, flutriafol, Phaltan, fosetyl, fosetyl sodium, fuberidazole, Furalaxyl, the spirit of furan pyrazoles, sterilizing amine, seed dressing amine, Guanoctine, Perchlorobenzene, own azoles alcohol, hymexazol, IMAZALIL, acid amides azoles, biguanide spicy acid salt, biguanide spicy acid salt, iodocarb, cycltebuconazole, iprobenfos, isopropyl is fixed, iprovalicarb, people's metamycin, isoprothiolane, chlorobenzene climbazole, kasugamycin, imines bacterium, zinc manganese ethylenebisdithiocarbamate, maneb, meferimzone, mepanipyrim, the third oxygen mebenil, metaxanin, Metalaxyl-M, encircle penta azoles bacterium, methasulfocarb, first methuroxam, Carbatene, fork phenalgin acid amides, metsulfovax, midolthromycin, nitrile bacterium azoles, myclozolin, myprozine, nicobifen, isopropyl disappears, noviflumuron, nuarimol, fenfuram, orysastrobin, the spirit of Evil frost, oxolinic acide, oxpoconazole, oxycarboxin, oxyfenthiin, paclobutrazol, pefurazoate, Topaze, pencycuron, two S-sevens, phthalide, ZEN 90160, pipron, polyoxin, polyoxorim, thiabendazole, Prochloraz, sterilization profit, hundred dimension spirits, propanosine-sodium, Wocosin 50TK, zinc 1,2-propylene bisdithiocarbamate, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, chlorine pyrrole furan ether, pyrrolenitrine, azoles oxolinic acide, quinoxyfen, quintozene, simeconazoles, the luxuriant amine of Luo Evil, sulphur, tebuconazole, tecloftalam, tecnazene, tetcyclacis, fluorine ether azoles, Apl-Luster, thicyofen, thifluzamide, thiophanate methyl, thiram, tioxymid, tolclofosmethyl, tolylfluanid, triazolone, Triabimeno I, fourth triazole, azoles bacterium piperazine, tricyclamide, tricyclazole, tridemorph, oxime bacterium ester, fluorine bacterium azoles, triforine, triticonazole, uniconazole, Validacin (Takeda), vinclozolin, zineb, ziram, zoxamide, (2S)-N-[2-[4-[[3-(4-chloro-phenyl-)-2-propynyl] oxygen]-3-p-methoxy-phenyl] ethyl]-3-methyl-2-[(methyl sulphonyl) amino] butyramide, 1-(1-naphthyl)-1H-pyrroles-2,5-diketone, 2,3,5,6-tetrachloro-4-(methyl sulphonyl) pyridine, 2-amino-4-methyl-N-phenyl-5-thiazole carboxamides, the chloro-N-of 2-(2,3-dihydro-1,1,3-trimethylammonium-1H-indenes-4-yl)-Niacinamide, 3,4,5-tri-is chloro-2,6-pyridine dintrile, actinovate, cis-1-(4-chloro-phenyl-)-2-(1H-1,2,4-triazol-1-yl) suberyl alcohol, 1-(2,3-dihydro-2,2-dimethyl-1H-indenes-1-yl)-1H-imidazole-5-carboxylic acid methyl esters, saleratus, N-(6-methoxyl group-3-pyridyl) cyclopropane carboxamide, N-butyl-8-(1,1-dimethyl ethyl)-1-oxaspiro [4.5] decane-3-amine, tetrathio sodium carbonate,
With mantoquita and preparation thereof, for example Bordeaux mixture, copper hydroxide, copper naphthenate, COPPER OXYCHLORIDE 37,5, copper sulfate, cufraneb, Red copper oxide, mancopper, oxinecopper.
Bactericide:
Bronopol, dichlorophen, N-Serve, nickel dimethyldithiocarbamate, kasugamycin, different thiophene bacterium ketone, carboxylic acid furans, terramycin, thiabendazole, Streptomycin sulphate, tecloftalam, copper sulfate and other copper agents.
Insecticide/miticide/nematocides:
Avermectin, ABG-9008, Ortho 12420, acequinocyl, pyrrole worm are clear, second phthalein worm eyeball, fluorine ester chrysanthemum ester, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, sulfone go out prestige, Pynamin, Pynamin 1R isomer, nail body Cypermethrin, amidoflumet, aminocarb, U-36059, Avrmectin, AZ-60541, Ai Zhading, azoles pyridine phosphorus, R-1582, triazotion, azoles ring tin,
Bacillus popilliae, Bacillus sphaericus, Ke opposes gram bacterium, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, baculovirus, beauveria bassiana, beauveria tenella, Evil worm prestige, benfuracarb, bensultap, benzoximate, β-cyfloxylate, Cypermethrin, Bifenazate, bifenthrin, Niagara 9044, Dtrans allethrin, Dtrans allethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistrifluron, BPMC, brofenprox, bromophos_ethyl, bromopropylate, bromobenzene alkene phosphorus (methyl), BTG-504, BTG-505, bufencarb, Buprofezin, special Pyrimitate, fourth fork prestige, oxygen fourth fork prestige, butyl pyridaben,
Cadusafos, toxaphene, SevinCarbaryl, carbofuran, carbophenothion, carbosulfan, Padan, CGA-50439, chinomethionate, Niran, chlordimeform, chloethocarb, earth worm chlorine phosphorus, fluorine azoles worm is clear, Zaprawa enolofos, UC 62644, chlormephos, G-23922, trichloronitromethane, chlorproxyfen, chlorpyrifos_methyl, Chlorpyrifos 94 (ethyl), chlovaporthrin, ring worm hydrazides, cis-Cypermethrin, cis-Chryson, cis-permethrin, cyhalothrin, cloethocarb, clofentezine, clothianidin, clothiazoben, Pherocon CM, Coumaphos, S-4087, cynock, cycloprene, cycloprothrin, Cydia pomonella, cyfloxylate, (RS) cyhalothrin, cyhexatin, Cypermethrin, phenylate permethrin (1R-trans-isomer(ide)), cyromazine,
DDT, Deltamethrin, methyl 1, dioxydemeton-s-methyl, kill that mite sulphur is grand, torak, diazinon, dichlofenthion, SD-1750, Mitigan, Carbicron, Dicyclanil, TH-6040, Rogor, dimethylvinphos, dinobuton, dinocap, the luxuriant ether of MTI-446, Evil, thiodemeton, iodoxy fourth two are pungent, benzene oxycetylene mite, DOWCO-439,
Eflusilanate, emaricin, emaricin benzoate, Prallethrin (1R isomer), 5a,6,9,9a-hexahydro-6,9-methano-2,4, entomophthora belong to kind, EPN, esfenvalerate, benzene worm prestige, ethiprole, Nialate, ethoprop, ether chrysanthemum ester, Te Ben oxazole, oxygen Pyrimithate,
Famophos, Nemacur, fenazaquin, fenbutatin oxide, fenfluthrin, Sumithion, Osbac, fenothiocarb, fenoxacrim, ABG-6215, Fenvalerate, must mite Garrick, fenpirithrin, fenpyroximate, fensulfothion, Tiguvon, fluorine nitre pentanoic, kill chrysanthemum ester, Frontline, flonicamid, fluacrypyrim, fluorine fluazuron, thiazole mite, brofluthrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, fluorine the third benzyl oxide, flumethrin, pyrrole fluorine sulphur phosphorus, flutiazin (fluorine mite piperazine), taufluvalinate, Dyfonate, formetanate, peace fruit, fosmethilan, thiazolone phosphorus, fubfenprox (halfenprox), furathiocarb,
Lindane, gossyplure, Grandemone, granulosis virus(GV),
Halogen ether chrysanthemum ester, RH 0345, HCH, HCN-801, heptan worm phosphorus, HEXAFLUMURON, hexythiazox, amdro, Entocon ZR 512,
IKA-2002, imidacloprid, Imiprothrin, oxadiazole worm, iodfenphos TOP, iprobenfos, fluorine azoles phosphorus, propylamine phosphorus, isoprocarb, isoxazoline, ivermectin,
japonilure、
Sai Evil chrysanthemum ester, nucleopolyhedrosis virus, illiteracy 7,
Cyhalothrin, lindane, fluorine the third oxygen urea,
Phosphothion, mecarbam, first oxydemeton_methyl, Halizan, metamsodium, methacrifos, acephatemet, green muscardine fungus, yellowish green green muscardine fungus, methidathion, metmercapturon, methomyl, Entocon ZR 515, methoxychlor, Runner, meta-tolyl-N-methylcarbamate (MTMC), metoxadiazone, Phosdrin, milbemycin, milbemycin, MKI-245, MON-45700, monocrotophos, Moxidectin, MTI-800,
Naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram, WL 35651, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Rimon, noviflumuron,
OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, thioxamyl, oxydemeton methyl,
Paecilomyces fumosoroseus, methyl parathion, one six zero five (ethyls), permethrin is (cis-, trans-), oil, PH-6045, phenothrin (1R trans-isomer(ide)), Tsidial, phorate, zolone, R-1504, phosphamidon, second the third phosphorus prestige, phoxim, piperonyl butoxide, Aphox, pirimiphosmethyl, pirimiphos ethyl, prallethrin, Profenofos, promecarb, Kayaphos, propargite, propetamphos, Propoxur, Toyodan, Fac, protrifenbute, pymetrozine, pyraclofos, anti-Chryson, pyrethrum, pyridaben, pyridalyl, Ofunack, pyridathion, pyramine phenylate, pyriproxyfen,
Quinalphos,
Chryson, RH-5849, ribavirin, RU-12457, RU-15525,
S-421, S-1833, salithion, cadusafos, SI-0009, deinsectization silicon ether, spinosad, spiral shell mite ester, Spiromesifen, sulfluramid, dithione, second Toyodan, SZI-121,
Taufluvalinate, RH-5992, tebufenpyrad, Tebupirimphos, volt worm phosphorus, tefluthrin, temephos, deinsectization fear, terbam, Terbufos, tetrachlorvinphos, tetradifon, Tetramethrin, Tetramethrin (1R isomer), Diphenylsulfide, pungent body Cypermethrin, thiacloprid (thiacloprid), Diacloden, moth fly nitrile, thiatriphos, thiocyclarn, UC-51762, special ammonia fork prestige, thiometon, disosultap, thuringiensin, tolfenpyrad, fluorine Deltamethrin, tralomethrin, transfluthrin, benzene match mite, triaxamate, triazophos, triazuron, trichlophenidine, Trichlorphon, desinsection is grand, trimethacarb,
Vamidothion, fluorine pyrazoles worm, verbutin, Verticillium lecanii,
WL-108477、WL-40027、
YI-5201、Y I-5301、YI-5302、
XMC, xylylcarb,
ZA-3274, own body Cypermethrin, zolaprofos, ZXI-8901,
Compound 3-aminomethyl phenyl carboxylamine propyl ester (meta-tolyl-N-methylcarbamate (MTMC) Z),
Compound 3-(5-chloro-3-pyridyl base)-8-(2,2,2-trifluoroethyl)-8-azabicyclo [3.2.1] octane-3-nitrile (CAS number of registration 185982-80-3) and corresponding 3-endo isomer (CAS number of registration 185984-60-5) (referring to WO-96/37494, WO-98/25923),
And include the preparation that kills insect active plant milk extract, nematode, fungi or virus.
Active compound that also can be known with other for example weedicide mixes, or mixes with fertilizer and growth regulator.
In addition, formula of the present invention (I) compound also has extraordinary anti-mycotic activity.This compounds has the antifungic action spectrum of non-constant width, particularly for dermatophytosis (dermatophyte) and yeast, mould and dimorphic fungus (diphasic fungi) are (for example, for Candida (Candida) bacterial classification, Candida albicans (Candida albicans) for example, Candida glabrata (Candida glabrata)), and cotton-shaped surperficial tinea bacterium (Epidermophyton floccosum), aspergillus (Aspergillus) bacterial classification, for example aspergillus niger (Aspergillus niger) and Aspergillus fumigatus (Aspergillus fumigatus), trichophyton (Trichophyton) bacterial classification, alpha fungus (Trichophyton mentagrophytes) for example,
Microsporon (Microsporon) bacterial classification is microsporum canis (Microsporon canis) and Microsporon audouinii for example.Listed fungi only for the purpose of illustration, and and the unrestricted fungi spectrum containing.
Active compound can itself, its dosage form or type of service prepared therefrom use, for example i.e. solution of use, suspension agent, wettable powder, paste, soluble powder, powder agent and granule.Use in a usual manner and carry out, such as watering, spraying, atomization, broadcast sowing (broadcasting), dust, foam, shed etc.Also can use active compound by ultra-low volume method (ultra-low-volume method), or active agent preparations or active compound itself are injected in soil.Also can process plant seed.
When active compound of the present invention is used as mycocide, rate of application can change according to using type in relatively wide scope.For the processing of plant parts, active compound rate of application is generally 0.1 to 10000g/ha, and preferably 10 to 1000g/ha.For seed dressing, active compound rate of application is generally 0.001 to 50g per kilogram seed, preferably 0.01 to 10g per kilogram seed.For soil treatment, active compound rate of application is generally 0.1 to 10000g/ha, and preferably 1 to 5000g/ha.
Preparation method and the purposes of active compound of the present invention are set forth by following examples.
Preparation Example
embodiment (I-1-a-1)
3.1g (8.0mmol) EXAMPLE V-1 compound is dissolved in 40mL anhydrous dimethyl formamide (DMF), under 10 ℃ of logical argon gas conditions, adds 1.08g (9.6mmol) potassium tert.-butoxide.Mixture stirring at room 12 hours, decompression is lower to desolventizing, and resistates is processed in the aqueous sodium hydroxide solution of 150mL 10%.Methylene dichloride 3 for mixture * extraction, water is at the cooling lower 2N hcl acidifying of using of ice bath.Methylene dichloride 3 for acid solution * extraction, then the organic phase water 1 of merging * washing uses dried over sodium sulfate.Decompression is lower to desolventizing, ether crystallization for resistates, suction filtration air-dry.
Productive rate: 2.3g (theoretical value 85%); Colorless solid; Temperature: 172 ℃
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-1-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
I-1-a-2 H CH 3 H 2-Cl 253
I-1-a-3 H CH 3 H 3-Cl 177
I-1-a-4 H CH 3 H 4-Cl 206
I-1-a-5 H CH 3 H 2-F 195
I-1-a-6 H CH 3 H 3-F 161
I-1-a-1 H CH 3 H 4-F 172
I-1-a-7 H CH 3 H 2-CH 3 153
I-1-a-8 H CH 3 H 3-CH 3 173
I-1-a-9 H CH 3 H 4-CH 3 168
I-1-a-10 H CH 3 H 2，3-Cl 2 207
I-1-a-1l H CH 3 H 2，4-Cl 2 161
I-1-a-12 H CH 3 H 2，5-Cl 2 150
I-1-a-13 H CH 3 H 3，4-Cl 2 207
I-1-a-14 H CH 3 H 3，5-Cl 2 196
I-1-a-15 H CH 3 H 2，4-F 2 173
I-1-a-16 H CH 3 H 2，5-F 2 197
I-1-a-17 H CH 3 H 3-Cl，4-F 192
I-1-a-18 H CH 3 H 2-CF 3 142
I-1-a-19 H CH 3 H 3-CF 3 185
I-1-a-20 H CH 3 H 4-CF 3 224
I-1-a-2l H CH 3 H 2-OCH 3 185
I-1-a-22 H CH 3 H 3-OCH 3 135
I-1-a-23 H CH 3 H 4-OCH 3 156
I-1-a-24 H CH 3 H 3-SO 2C 2H 5 202
I-1-a-25 H CH 3 H 4-SO 2C 2H 5 197
I-1-a-26 H CH 3 H 3-NO 2 202
I-1-a-27 H CH 3 H 4-OCF 3 151
I-1-a-28 H CH 3 H 4-OPh 204
I-1-a-29 H CH 3 H 4-SCH 3 156
I-1-a-30 H CH 3 H 4-i-C 3H 7 142
I-1-a-31 H CH 3 H 3，5-(CF 3) 2 254
I-1-a-32 CH 3 CH 3 CH 3 4-F Oily matter
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
I-1-a-33 H CH 3 CH 3 4-Cl 101
I-1-a-34 CH 3 CH 3 H 4-F 246
I-1-a-35 CH 3 CH 3 H 4-Cl 240
I-1-a-36 CH 3 CH 3 CH 3 4-Cl ＞250
I-1-a-37 H Cl H 4-CF 3 257
I-1-a-38 H Cl H 4-Cl 229
I-1-a-39 H Cl H 4-F 187
I-1-a-40 H Cl H 3，4-Cl 2 201
I-1-a-41 H Cl H 2，4-Cl 2 184
I-1-a-42 H Cl H 2，4-F 2 200
I-1-a-43 H Cl H 3，5-Cl 2 256
I-1-a-44 H Cl H 4-F，3-Cl 228
I-1-a-45 H Cl H 2，5-Cl 2 177
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-2-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
I-2-a-1 H CH 3 H 2-Cl 204
I-2-a-2 H CH 3 H 3-Cl 167
I-2-a-3 H CH 3 H 4-Cl 207
I-2-a-4 H CH 3 H 2-F 179
I-2-a-5 H CH 3 H 3-F 175
I-2-a-6 H CH 3 H 4-F 188
I-2-a-7 H CH 3 H 2-CH 3 172
I-2-a-8 H CH 3 H 3-CH 3 175
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
I-2-a-9 H CH 3 H 4-CH 3 176
I-2-a-10 H CH 3 H 2，3-Cl 2 192
I-2-a-11 H CH 3 H 2，4-Cl 2 176
I-2-a-12 H CH 3 H 2，5-Cl 2 149
I-2-a-13 H CH 3 H 3，4-Cl 2 191
I-2-a-14 H CH 3 H 3，5-Cl 2 187
I-2-a-15 H CH 3 H 2，4-F 2 191
I-2-a-16 H CH 3 H 2，5-F 2 182
I-2-a-17 H CH 3 H 3-Cl，4-F 201
I-2-a-18 H CH 3 H 2-CF 3 142
I-2-a-19 H CH 3 H 3-CF 3 180
I-2-a-20 H CH 3 H 4-CF 3 221
I-2-a-21 H CH 3 H 2-OCH 3 158
I-2-a-22 H CH 3 H 3-OCH 3 158
I-2-a-23 H CH 3 H 4-OCH 3 186
I-2-a-24 H CH 3 H 3-SO 2C 2H 5 189
I-2-a-25 H CH 3 H 4-SO 2C 2H 5 226
I-2-a-26 H CH 3 H 3-NO 2 205
I-2-a-27 H CH 3 H 4-OCF 3 198
I-2-a-28 H CH 3 H 4-OPh 226
I-2-a-29 H CH 3 H 4-SCH 3 176
I-2-a-30 H CH 3 H 4-i-C 3H 7 170
I-2-a-31 H CH 3 H 3，5-(CF 3) 2 223
I-2-a-32 CH 3 CH 3 CH 3 4-F Oily matter
I-2-a-33 H CH 3 CH 3 4-Cl 185
I-2-a-34 CH 3 CH 3 H 4-F 213
I-2-a-35 CH 3 CH 3 H 4-Cl 255
I-2-a-36 CH 3 CH 3 CH 3 4-Cl 244
I-2-a-37 H Cl H 4-CF 3 251
I-2-a-38 H Cl H 4-Cl 227
I-2-a-39 H Cl H 4-F 186
1-2-a-40 H Cl H 2，4-Cl 2 192
I-2-a-41 H Cl H 3，4-Cl 2 234
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
I-2-a-42 H Cl H 2，4-F 2 227
I-2-a-43 H Cl H 3，5-Cl 2 253
I-2-a-44 H Cl H 4-F，3-Cl 234
I-2-a-45 H Cl H 2，5-Cl 2 198
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-3-a) compound:
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-4-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point ℃
I-4-a-1 H CH 3 H 4-F 151
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-5-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point ℃
I-5-a-1 H CH 3 H 4-F 184
I-5-a-2 H CH 3 H 4-Cl 33
I-5-a-3 H Cl H 4-F 219
I-4-a-4 H Cl H 4-Cl 220
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-6-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point ℃
I-6-a-1 H CH 3 H 4-F 164
I-6-a-2 H CH 3 H 4-Cl 130
I-6-a-3 H Cl H 4-Cl 156
I-6-a-4 H Cl H 4-F 161
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-7-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point ℃
I-7-a-1 H CH 3 H 4-F 150
I-7-a-2 H CH 3 H 4-Cl 160
I-7-a-3 H Cl H 4-F 166
I-7-a-4 H Cl H 4-Cl 139
To be similar to the method for embodiment (I-1-a-1), and in a word bright according to preparation formula (I) compound, preparation is with following formula (I-8-a) compound:
Embodiment numbering W X Y V 1/V 2 Fusing point ℃
I-8-a-1 H CH 3 H 4-Cl 210
I-8-a-2 H Cl H 4-Cl 130
example I-1-b-1
Under room temperature, by triacetamide (0.17g; 1.63mmol) and trimethyl-acetyl chloride (0.2g; Methylene dichloride 1.63mmol) (10ml) solution is added to successively 0.5g (1.48mmol) example I-1-a-1 compound and is dissolved in the solution of 20ml methylene dichloride.After stirring at room 12 hours, 100ml methylene dichloride dilution for mixture, uses respectively 10% citric acid and 10% aqueous sodium hydroxide solution 1 * washing.Organic phase dried over sodium sulfate, decompression is lower to desolventizing, sherwood oil crystallization for resistates, suction filtration air-dry.
Productive rate: 0.35g (theoretical value 56%); Colorless solid; 188 ℃ of fusing points.
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-1-b) compound:
Embodiment numbering W X Y V 1/V 2 R 1 Fusing point (℃)
I-1-b-2 H CH 3 H 2-Cl t-C 4H 9 Oily matter
I-1-b-3 H CH 3 H 3-Cl t-C 4H 9 Oily matter
I-1-b-4 H CH 3 H 4-Cl t-C 4H 9 Oily matter
I-1-b-5 H CH 3 H 2-F t-C 4H 9 Oily matter
Embodiment numbering W X Y V 1/V 2 R 1 Fusing point (℃)
I-1-b-6 H CH 3 H 3-F t-C 4H 9 Oily matter
I-1-b-1 H CH 3 H 4-F t-C 4H 9 188
I-1-b-7 H CH 3 H 2-CH 3 t-C 4H 9 Oily matter
I-1-b-8 H CH 3 H 3-CH 3 t-C 4H 9 Oily matter
I-1-b-9 H CH 3 H 4-CH 3 t-C 4H 9 Oily matter
I-1-b-10 H CH 3 H 2，3-Cl 2 t-C 4H 9 Oily matter
I-1-b-11 H CH 3 H 2，4-Cl 2 t-C 4H 9 Oily matter
I-1-b-12 H CH 3 H 2，5-Cl 2 t-C 4H 9 Oily matter
I-1-b-13 H CH 3 H 3，4-Cl 2 t-C 4H 9 Oily matter
I-1-b-14 H CH 3 H 3，5-Cl 2 t-C 4H 9 Oily matter
I-1-b-15 H CH 3 H 2，4-F 2 t-C 4H 9 187
I-1-b-16 H CH 3 H 2，5-F 2 t-C 4H 9 Oily matter
I-1-b-17 H CH 3 H 3-Cl，4-F t-C 4H 9 Oily matter
I-1-b-18 H CH 3 H 2-CF 3 t-C 4H 9 Oily matter
I-1-b-19 H CH 3 H 3-CF 3 t-C 4H 9 Oily matter
I-1-b-20 H CH 3 H 4-CF 3 t-C 4H 9 175
I-1-b-21 H CH 3 H 2-OCH 3 t-C 4H 9 Oily matter
I-1-b-22 H CH 3 H 3-OCH 3 t-C 4H 9 Oily matter
I-1-b-23 H CH 3 H 4-OCH 3 t-C 4H 9 Oily matter
I-1-b-24 H CH 3 H 3-SO 2C 2H 5 t-C 4H 9 Oily matter
I-1-b-25 H CH 3 H 4-SO 2C 2H 5 t-C 4H 9 Oily matter
I-1-b-26 H CH 3 H 3-NO 2 t-C 4H 9 Oily matter
I-1-b-27 H CH 3 H 4-OCF 3 t-C 4H 9 Oily matter
I-1-b-28 H CH 3 H 4-OPh t-C 4H 9 Oily matter
I-1-b-29 H CH 3 H 4-SCH 3 t-C 4H 9 Oily matter
I-1-b-30 H CH 3 H 4-i-C 3H 7 t-C 4H 9 Oily matter
I-1-b-31 H CH 3 H 3，5-(CF 3) 2 t-C 4H 9 Oily matter
I-1-b-32 H CH 3 H 4-Cl i-C 3H 7 Oily matter
I-1-b-33 H CH 3 H 4-F c-C 3H 5 Oily matter
I-1-b-34 CH 3 CH 3 CH 3 4-F t-C 4H 9 Oily matter
I-1-b-35 H CH 3 CH 3 4-Cl t-C 4H 9 Oily matter
I-1-b-36 CH 3 CH 3 H 4-Cl t-C 4H 9 69
I-1-b-37 CH 3 CH 3 H 4-F t-C 4H 9 Oily matter
Embodiment numbering W X Y V 1/V 2 R 1 Fusing point (℃)
I-1-b-38 CH 3 CH 3 H 4-Cl i-C 3H 7 Oily matter
I-1-b-39 CH 3 CH 3 H 4-F i-C 3H 7 Oily matter
I-1-b-40 CH 3 CH 3 CH 3 4-Cl t-C 4H 9 35
I-1-b-41 CH 3 CH 3 CH 3 4-Cl i-C 3H 7 138
I-1-b-42 H CH 3 H 3-OCH 3 c-C 3H 5 Oily matter
I-1-b-43 H CH 3 H 3-OCH 3 i-C 3H 7 Oily matter
I-1-b-44 H Cl H 4-CF 3 t-C 4H 9 Oily matter
I-1-b-45 H Cl H 4-Cl t-C 4H 9 Oily matter
I-1-b-46 H Cl H 4-F t-C 4H 9 46
I-1-b-47 H Cl H 4-Cl CH 3 Oily matter
I-1-b-48 H Cl H 4-Cl C 2H 5 Oily matter
I-1-b-49 H Cl H 4-Cl i-C 3H 7 Oily matter
I-1-b-50 H Cl H 4-Cl c-C 3H 5 Oily matter
I-1-b-51 H Cl H 2，4-Cl 2 t-C 4H 9 Oily matter
I-1-b-52 H Cl H 3，4-Cl 2 t-C 4H 9 Oily matter
I-1-b-53 H Cl H 3，5-Cl 2 t-C 4H 9 Oily matter
I-1-b-54 H Cl H 2，4-F 2 t-C 4H 9 Oily matter
I-1-b-55 H Cl H 3-Cl，4-F t-C 4H 9 Oily matter
I-1-b-56 H Cl H 2-Cl，5-Cl t-C 4H 9 Oily matter
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-2-b) compound:
Embodiment numbering W X Y V 1/V 2 R 1 Fusing point (℃)
I-2-b-1 H CH 3 H 2-Cl t-C 4H 9 Oily matter
I-2-b-2 H CH 3 H 3-Cl t-C 4H 9 Oily matter
I-2-b-3 H CH 3 H 4-Cl t-C 4H 9 Oily matter
I-2-b-4 H CH 3 H 2-F t-C 4H 9 Oily matter
I-2-b-5 H CH 3 H 3-F t-C 4H 9 Oily matter
I-2-b-6 H CH 3 H 4-F t-C 4H 9 Oily matter
I-2-b-7 H CH 3 H 2-CH 3 t-C 4H 9 Oily matter
I-2-b-8 H CH 3 H 3-CH 3 t-C 4H 9 Oily matter
I-2-b-9 H CH 3 H 4-CH 3 t-C 4H 9 Oily matter
I-2-b-10 H CH 3 H 2，3-Cl 2 t-C 4H 9 155
I-2-b-11 H CH 3 H 2，4-Cl 2 t-C 4H 9 117
I-2-b-12 H CH 3 H 2，5-Cl 2 t-C 4H 9 Oily matter
I-2-b-13 H CH 3 H 3，4-Cl 2 t-C 4H 9 Oily matter
I-2-b-14 H CH 3 H 3，5-Cl 2 t-C 4H 9 Oily matter
I-2-b-15 H CH 3 H 2，4-F 2 t-C 4H 9 174
I-2-b-16 H CH 3 H 2，5-F 2 t-C 4H 9 184
I-2-b-17 H CH 3 H 3-Cl，4-F t-C 4H 9 Oily matter
I-2-b-18 H CH 3 H 2-CF 3 t-C 4H 9 Oily matter
I-2-b-19 H CH 3 H 3-CF 3 t-C 4H 9 Oily matter
I-2-b-20 H CH 3 H 4-CF 3 t-C 4H 9 187
I-2-b-21 H CH 3 H 2-OCH 3 t-C 4H 9 Oily matter
I-2-b-22 H CH 3 H 3-OCH 3 t-C 4H 9 Oily matter
I-2-b-23 H CH 3 H 4-OCH 3 t-C 4H 9 Oily matter
I-2-b-24 H CH 3 H 3-SO 2C 2H 5 t-C 4H 9 Oily matter
I-2-b-25 H CH 3 H 4-SO 2C 2H 5 t-C 4H 9 Oily matter
I-2-b-26 H CH 3 H 3-NO 2 t-C 4H 9 Oily matter
I-2-b-27 H CH 3 H 4-OCF 3 t-C 4H 9 Oily matter
I-2-b-28 H CH 3 H 4-OPh t-C 4H 9 104
I-2-b-29 H CH 3 H 4-SCH 3 t-C 4H 9 176
I-2-b-30 H CH 3 H 4-i-C 3H 7 t-C 4H 9 138
I-2-b-31 H CH 3 H 4-Cl i-C 3H 7 129
I-2-b-32 CH 3 CH 3 CH 3 4-F t-C 4H 9 Oily matter
I-2-b-33 H CH 3 CH 3 4-Cl t-C 4H 9 105
Embodiment numbering W X Y V 1/V 2 R 1 Fusing point (℃)
I-2-b-34 CH 3 CH 3 H 4-Cl t-C 4H 9 52
I-2-b-35 CH 3 CH 3 H 4-F t-C 4H 9 Oily matter
I-2-b-36 CH 3 CH 3 H 4-F i-C 3H 7 Oily matter
I-2-b-37 CH 3 CH 3 CH 3 4-Cl t-C 4H 9 Oily matter
I-2-b-38 H CH 3 H 2，4-Cl 2 i-C 3H 7 Oily matter
I-2-b-39 H CH 3 H 2，4-Cl 2 c-C 3H 5 Oily matter
I-2-b-40 H Cl H 4-CF 3 t-C 4H 9 Oily matter
I-2-b-41 H Cl H 4-Cl t-C 4H 9 Oily matter
I-2-b-42 H Cl H 4-F t-C 4H 9 Oily matter
I-2-b-43 H Cl H 4-Cl CH 3 171
I-2-b-44 H Cl H 4-Cl C 2H 5 183
I-2-b-45 H Cl H 4-Cl i-C 3H 7 189
I-2-b-46 H Cl H 4-Cl c-C 3H 5 172
I-2-b-47 H Cl H 2，4-Cl 2 t-C 4H 9 Oily matter
I-2-b-48 H Cl H 3，4-Cl 2 t-C 4H 9 103
I-2-b-49 H Cl H 3，5-Cl 2 t-C 4H 9 168
I-2-b-50 H Cl H 3-Cl，4-F t-C 4H 9 90
I-2-b-51 H Cl H 2，5-Cl 2 t-C 4H 9 Oily matter
I-2-b-52 H Cl H 2，4-F 2 t-C 4H 9 Oily matter
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-3-b) compound:
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-4-b) compound:
Embodiment numbering W X Y V 2/V 2 R 1 Fusing point ℃
I-4-b-1 H CH 3 H 4-F t-C 4H 9 158-160
I-4-b-2 H CH 3 Cl 4-Cl t-C 4H 9 Oily matter
I-4-b-3 H Cl H 4-F t-C 4H 9 Oily matter
I-4-b-4 H Cl H 4-Cl t-C 4H 9 Oily matter
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-5-b) compound:
Embodiment numbering W X Y V 2/V 2 R 1 Fusing point ℃
I-5-b-1 H CH 3 H 4-F t-C 4H 9 123-124
I-5-b-2 H CH 3 H 4-Cl t-C 4H 9 Oily matter
I-5-b-3 H Cl H 4-F t-C 4H 9 43-44
I-5-b-4 H Cl H 4-Cl t-C 4H 9 44-45
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-6-b) compound:
Embodiment numbering W X Y V 2/V 2 R 1 Fusing point ℃
I-6-b-1 H CH 3 H 4-F t-C 4H 9 85
I-6-b-2 H CH 3 H 4-Cl t-C 4H 9 43
I-6-b-3 H Cl H 4-F t-C 4H 9 Oily matter
I-6-b-4 H Cl H 4-Cl t-C 4H 9 Oily matter
To be similar to the method for embodiment (I-1-b-1), and in a word bright according to preparation formula (I-b) compound, preparation is with following formula (I-7-b) compound:
Embodiment numbering W X Y V 2/V 2 R 1 Fusing point ℃
I-7-b-1 H CH 3 H 4-Cl t-C 4H 9 206
I-7-b-2 H Cl H 4-Cl t-C 4H 9 Oily matter
example I-1-c-1
Under room temperature, by triethylamine (0.13g; 1.3 μ mol) and Vinyl chloroformate (0.14g; 1.3 μ mol) solution that is dissolved in 10ml methylene dichloride is added to successively 0.4g (1.2mmol) embodiment (I-a-1) compound and is dissolved in the solution of 20ml methylene dichloride.After stirring at room 12 hours, 100ml methylene dichloride dilution for mixture, uses respectively 10% citric acid and 10% aqueous sodium hydroxide solution 1 * washing.Organic phase dried over sodium sulfate, decompression is lower to desolventizing.
Productive rate: 0.45g (theoretical value 94%); Light brown oily thing.
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-1-c) compound:
Embodiment numbering W X Y V 1V 2 M R 2 Fusing point (℃)
I-1-c-2 H CH 3 H 2-Cl O C 2H 5 Oily matter
I-1-c-3 H CH 3 H 3-Cl O C 2H 5 172
I-1-c-4 H CH 3 H 4-Cl O C 2H 5 Oily matter
I-1-c-5 H CH 3 H 2-F O C 2H 5 Oily matter
I-1-c-6 H CH 3 H 3-F O C 2H 5 Oily matter
I-1-c-1 H CH 3 H 4-F O C 2H 5 Oily matter
I-1-c-7 H CH 3 H 2-CH 3 O C 2H 5 170
I-1-c-8 H CH 3 H 3-CH 3 O C 2H 5 Oily matter
I-1-c-9 H CH 3 H 4-CH 3 O C 2H 5 Oily matter
I-1-c-10 H CH 3 H 2，3-Cl 2 O C 2H 5 Oily matter
I-1-c-11 H CH 3 H 2，4-Cl 2 O C 2H 5 Oily matter
I-1-c-12 H CH 3 H 2，5-Cl 2 O C 2H 5 Oily matter
I-1-c-13 H CH 3 H 3，4-Cl 2 O C 2H 5 Oily matter
I-1-c-14 H CH 3 H 3，5-Cl 2 O C 2H 5 Oily matter
I-1-c-15 H CH 3 H 2，4-F 2 O C 2H 5 Oily matter
I-1-c-16 H CH 3 H 2，5-F 2 O C 2H 5 Oily matter
I-1-c-17 H CH 3 H 3-Cl，4-F O C 2H 5 Oily matter
I-1-c-18 H CH 3 H 3-CF 3 O C 2H 5 Oily matter
I-1-c-19 H CH 3 H 4-CF 3 O C 2H 5 Oily matter
I-1-c-20 H CH 3 H 2-OCH 3 O C 2H 5 Oily matter
I-1-c-21 H CH 3 H 3-OCH 3 O C 2H 5 Oily matter
I-1-c-22 H CH 3 H 3-SO 2C 2H 5 O C 2H 5 Oily matter
Embodiment numbering W X Y V 1V 2 M R 2 Fusing point (℃)
I-1-c-23 H CH 3 H 4-SO 2C 2H 5 O C 2H 5 Oily matter
I-1-c-24 H CH 3 H 4-OPh O C 2H 5 81
I-1-c-25 H CH 3 H 4-SCH 3 O C 2H 5 Oily matter
I-1-c-26 H CH 3 H 4-i-C 3H 7 O C 2H 5 Oily matter
I-1-c-27 H CH 3 CH 3 4-Cl O C 2H 5 Oily matter
I-1-c-28 CH 3 CH 3 H 4-Cl O C 2H 5 Oily matter
I-1-c-29 CH 3 CH 3 CH 3 4-Cl O C 2H 5 38
I-1-c-30 CH 3 CH 3 H 4-F O C 2H 5 Oily matter
I-1-c-31 H CH 3 H 3-OCH 3 O H 5C 2O-(CH 2) 2- Oily matter
I-1-c-32 H CH 3 H 4-Cl O C 2H 5 53
I-1-c-33 H Cl H 4-F O C 2H 5 Oily matter
I-1-c-34 H Cl H 4-Cl O CH 3 Oily matter
I-1-c-35 H Cl H 4-Cl O H 5C 2-O-(CH 2) 2- Oily matter
I-1-c-36 H Cl H 3，4-Cl 2 O C 2H 5 Oily matter
I-1-c-37 H Cl H 3，5-Cl 2 O C 2H 5 Oily matter
I-1-c-38 H Cl H 2，4-F 2 O C 2H 5 Oily matter
I-1-c-39 H Cl H 2，5-Cl 2 O C 2H 5 201
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-2-c) compound:
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point (℃)
I-2-c-1 H CH 3 H 2-Cl O C 2H 5 Oily matter
I-2-c-2 H CH 3 H 3-Cl O C 2H 5 Oily matter
I-2-c-3 H CH 3 H 4-Cl O C 2H 5 Oily matter
I-2-c-4 H CH 3 H 2-F O C 2H 5 Oily matter
I-2-c-5 H CH 3 H 3-F O C 2H 5 Oily matter
I-2-c-6 H CH 3 H 4-F O C 2H 5 Oily matter
I-2-c-7 H CH 3 H 2-CH 3 O C 2H 5 Oily matter
I-2-c-8 H CH 3 H 3-CH 3 O C 2H 5 Oily matter
I-2-c-9 H CH 3 H 4-CH 3 O C 2H 5 Oily matter
I-2-c-10 H CH 3 H 2，3-Cl 2 O C 2H 5 178
I-2-c-11 H CH 3 H 2，4-Cl 2 O C 2H 5 Oily matter
I-2-c-12 H CH 3 H 2，5-Cl 2 O C 2H 5 Oily matter
I-2-c-13 H CH 3 H 3，4-Cl 2 O C 2H 5 Oily matter
I-2-c-14 H CH 3 H 3，5-Cl 2 O C 2H 5 Oily matter
I-2-c-15 H CH 3 H 2，4-F 2 O C 2H 5 120
I-2-c-16 H CH 3 H 2，5-F 2 O C 2H 5 Oily matter
I-2-c-17 H CH 3 H 3-Cl，4-F O C 2H 5 Oily matter
I-2-c-18 H CH 3 H 2-CF 3 O C 2H 5 172
I-2-c-19 H CH 3 H 3-CF 3 O C 2H 5 Oily matter
I-2-c-20 H CH 3 H 4-CF 3 O C 2H 5 111
I-2-c-21 H CH 3 H 2-OCH 3 O C 2H 5 Oily matter
I-2-c-22 H CH 3 H 3-OCH 3 O C 2H 5 Oily matter
I-2-c-23 H CH 3 H 4-OCH 3 O C 2H 5 Oily matter
I-2-c-24 H CH 3 H 3-SO 2C 2H 5 O C 2H 5 Oily matter
I-2-c-25 H CH 3 H 4-SO 2C 2H 5 O C 2H 5 Oily matter
I-2-c-26 H CH 3 H 3-NO 2 O C 2H 5 Oily matter
I-2-c-27 H CH 3 H 4-OCF 3 O C 2H 5 Oily matter
I-2-c-28 H CH 3 H 4-OPh O C 2H 5 Oily matter
I-2-c-29 H CH 3 H 4-SCH 3 O C 2H 5 131
I-2-c-30 H CH 3 H 4-i-C 3H 7 O C 2H 5 Oily matter
I-2-c-31 H CH 3 H 3，5-(CF 3) 2 O C 2H 5 Oily matter
I-2-c-32 H CH 3 CH 3 4-Cl O C 2H 5 53
I-2-c-33 CH 3 CH 3 H 4-Cl O C 2H 5 Oily matter
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point (℃)
I-2-c-34 CH 3 CH 3 H 4-F O C 2H 5 Oily matter
I-2-c-35 H CH 3 H 2，4-Cl 2 O C 2H 5 Oily matter
I-2-c-36 H Cl H 4-F O C 2H 5 Oily matter
I-2-c-37 H Cl H 4-Cl O C 2H 5 Oily matter
I-2-c-38 H Cl H 4-Cl O CH 3 198
I-2-c-39 H Cl H 4-Cl O H 5C 2-O-(CH 2) 2- Oily matter
I-2-c-40 H Cl H 3，5-Cl 2 O C 2H 5 150
I-2-c-41 H Cl H 2，4-F 2 O C 2H 5 Oily matter
I-2-c-42 H Cl H 2，5-Cl 2 O C 2H 5 50
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-3-c) compound:
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-4-c) compound:
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point ℃
I-4-c-1 H CH 3 H 4-F O C 2H 5 Oily matter
I-4-c-2 H Cl H 4-Cl O C 2H 5 Oily matter
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-5-c) compound:
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point ℃
I-5-c-1 H CH 3 H 4-F O C 2H 5 Oily matter
I-5-c-2 H CH 3 H 4-Cl O C 2H 5 Oily matter
I-5-c-3 H Cl H 4-F O C 2H 5 Oily matter
I-5-c-4 H Cl H 4-Cl O C 2H 5 Oily matter
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-6-c) compound:
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point ℃
I-6-c-1 H Cl H 4-Cl O C 2H 5 Oily matter
To be similar to the method for embodiment (I-1-c-1), and in a word bright according to preparation formula (I-c) compound, preparation is with following formula (I-7-c) compound:
Embodiment numbering W X Y V 1/V 2 M R 2 Fusing point ℃
I-7-c-1 H CH 3 H 4-Cl O C 2H 5 25
I-7-c-1 H Cl H 4-Cl O C 2H 5 26
example I-d-1
Under room temperature, by triethylamine (0.13g; 1.3mmol) and ethyl chloride (0.17g; The solution that 1.3mmol) is dissolved in 10ml methylene dichloride is added to successively 0.4g (1.2mmol) embodiment (I-1-a-1) and is dissolved in the solution of 20ml methylene dichloride.After stirring at room 10 hours, 100ml methylene dichloride dilution for mixture, uses respectively 10% citric acid and 10% aqueous sodium hydroxide solution 1 * washing.Organic phase dried over sodium sulfate, decompression is lower to desolventizing.
Productive rate: 0.4g (theoretical value 70%); Light brown oily thing.
To be similar to the method for embodiment (I-d-1), and in a word bright according to preparation method, preparation is with following formula (I-d) compound:
eXAMPLE V-1-1
By 1.04g (5.3mmol) abe dissolved in 30ml methylene dichloride, splash into successively triethylamine and the 1.4g (5.3mmol) of 1.2g (11.8 μ mol) bbe dissolved in the solution of 20ml methylene dichloride.Mixture stirring at room 12 hours, adds 100ml methylene dichloride, uses respectively 2N hydrochloric acid and water 1 * purging compound.Organic phase dried over sodium sulfate, filters and reduces pressure down concentrated.
Productive rate: 2g (theoretical value 98%); Yellow oil, purifying is not for following reaction.
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-1) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point (℃)
V-1-2 H CH 3 H 2-Cl C 2H 5 Oily matter
V-1-3 H CH 3 H 3-Cl C 2H 5 Oily matter
V-1-4 H CH 3 H 4-Cl C 2H 5 Oily matter
V-1-5 H CH 3 H 2-F C 2H 5 Oily matter
V-1-6 H CH 3 H 3-F C 2H 5 Oily matter
V-1-1 H CH 3 H 4-F C 2H 5 Oily matter
V-1-7 H CH 3 H 2-CH 3 C 2H 5 Oily matter
V-1-8 H CH 3 H 3-CH 3 C 2H 5 Oily matter
V-1-9 H CH 3 H 4-CH 3 C 2H 5 Oily matter
V-1-10 H CH 3 H 2，3-Cl 2 C 2H 5 Oily matter
V-1-11 H CH 3 H 2，4-Cl 2 C 2H 5 Oily matter
V-1-12 H CH 3 H 2，5-Cl 2 C 2H 5 Oily matter
V-1-13 H CH 3 H 3，4-Cl 2 C 2H 5 Oily matter
V-1-14 H CH 3 H 3，5-Cl 2 C 2H 5 Oily matter
V-1-15 H CH 3 H 2，4-F 2 C 2H 5 Oily matter
V-1-16 H CH 3 H 2，5-F 2 C 2H 5 Oily matter
V-1-17 H CH 3 H 3-Cl，4-F C 2H 5 Oily matter
V-1-18 H CH 3 H 2-CF 3 C 2H 5 Oily matter
V-1-19 H CH 3 H 3-CF 3 C 2H 5 Oily matter
V-1-20 H CH 3 H 4-CF 3 C 2H 5 Oily matter
V-1-21 H CH 3 H 2-OCH 3 C 2H 5 Oily matter
V-1-22 H CH 3 H 3-OCH 3 C 2H 5 Oily matter
V-1-23 H CH 3 H 4-OCH 3 C 2H 5 Oily matter
V-1-24 H CH 3 H 3-SO 2C 2H 5 C 2H 5 Oily matter
V-1-25 H CH 3 H 4-SO 2C 2H 5 C 2H 5 Oily matter
V-1-26 H CH 3 H 3-NO 2 C 2H 5 Oily matter
V-1-27 H CH 3 H 4-OCF 3 C 2H 5 Oily matter
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point (℃)
V-1-28 H CH 3 H 4-OPh C 2H 5 Oily matter
V-1-29 H CH 3 H 4-SCH 3 C 2H 5 Oily matter
V-1-30 H CH 3 H 4-i-C 3H 7 C 2H 5 Oily matter
V-1-31 H CH 3 H 3，5-(CF 3) 2 C 2H 5 Oily matter
V-1-32 CH 3 CH 3 CH 3 4-F C 2H 5 Oily matter
V-1-33 H CH 3 CH 3 4-Cl C 2H 5 Oily matter
V-1-34 CH 3 CH 3 H 4-F C 2H 5 Oily matter
V-1-35 CH 3 CH 3 H 4-Cl C 2H 5 Oily matter
V-1-36 CH 3 CH 3 CH 3 4-Cl C 2H 5 Oily matter
V-1-37 H Cl H 4-F C 2H 5 Oily matter
V-1-38 H Cl H 4-Cl C 2H 5 Oily matter
V-1-39 H Cl H 4-CF 3 C 2H 5 Oily matter
V-1-40 H Cl H 2，4-Cl 2 C 2H 5 Oily matter
V-1-41 H Cl H 3，4-Cl 2 C 2H 5 65
V-1-42 H Cl H 3，5-Cl 2 C 2H 5 Oily matter
V-1-43 H Cl H 2，4-F 2 C 2H 5 Oily matter
V-1-44 H Cl H 3-Cl，4-F C 2H 5 Oily matter
V-1-45 H Cl H 2，5-Cl 2 C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-2) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point (℃)
V-2-1 H CH 3 H 2-Cl C 2H 5 Oily matter
V-2-2 H CH 3 H 3-Cl C 2H 5 Oily matter
V-2-3 H CH 3 H 4-Cl C 2H 5 Oily matter
V-2-4 H CH 3 H 2-F C 2H 5 Oily matter
V-2-5 H CH 3 H 3-F C 2H 5 Oily matter
V-2-6 H CH 3 H 4-F C 2H 5 Oily matter
V-2-7 H CH 3 H 2-CH 3 C 2H 5 Oily matter
V-2-8 H CH 3 H 3-CH 3 C 2H 5 Oily matter
V-2-9 H CH 3 H 4-CH 3 C 2H 5 Oily matter
V-2-10 H CH 3 H 2，3-Cl 2 C 2H 5 Oily matter
V-2-11 H CH 3 H 2，4-Cl 2 C 2H 5 Oily matter
V-2-12 H CH 3 H 2，5-Cl 2 C 2H 5 Oily matter
V-2-13 H CH 3 H 3，4-Cl 2 C 2H 5 Oily matter
V-2-14 H CH 3 H 3，5-Cl 2 C 2H 5 Oily matter
V-2-15 H CH 3 H 2，4-F 2 C 2H 5 Oily matter
V-2-16 H CH 3 H 2，5-F 2 C 2H 5 Oily matter
V-2-17 H CH 3 H 3-Cl，4-F C 2H 5 Oily matter
V-2-18 H CH 3 H 2-CF 3 C 2H 5 Oily matter
V-2-19 H CH 3 H 3-CF 3 C 2H 5 Oily matter
V-2-20 H CH 3 H 4-CF 3 C 2H 5 Oily matter
V-2-21 H CH 3 H 2-OCH 3 C 2H 5 Oily matter
V-2-22 H CH 3 H 3-OCH 3 C 2H 5 Oily matter
V-2-23 H CH 3 H 4-OCH 3 C 2H 5 Oily matter
V-2-24 H CH 3 H 3-SO 2C 2H 5 C 2H 5 Oily matter
V-2-25 H CH 3 H 4-SO 2C 2H 5 C 2H 5 Oily matter
V-2-26 H CH 3 H 3-NO 2 C 2H 5 Oily matter
V-2-27 H CH 3 H 4-OCF 3 C 2H 5 Oily matter
V-2-28 H CH 3 H 4-OPh C 2H 5 Oily matter
V-2-29 H CH 3 H 4-SCH 3 C 2H 5 Oily matter
V-2-30 H CH 3 H 4-i-C 3H 7 C 2H 5 Oily matter
V-2-31 H CH 3 H 3，5-(CF 3) 2 C 2H 5 Oily matter
V-2-32 CH 3 CH 3 CH 3 4-F C 2H 5 Oily matter
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point (℃)
V-2-33 H CH 3 CH 3 4-Cl C 2H 5 Oily matter
V-2-34 CH 3 CH 3 H 4-F C 2H 5 Oily matter
V-2-35 CH 3 CH 3 H 4-Cl C 2H 5 Oily matter
V-2-36 CH 3 CH 3 CH 3 4-Cl C 2H 5 Oily matter
V-2-37 H Cl H 4-F C 2H 5 Oily matter
V-2-38 H Cl H 4-Cl C 2H 5 Oily matter
V-2-39 H Cl H 4-CF 3 C 2H 5 Oily matter
V-2-40 H Cl H 2，4-Cl 2 C 2H 5 Oily matter
V-2-41 H Cl H 3，4-Cl 2 C 2H 5 Oily matter
V-2-42 H Cl H 3，5-Cl 2 C 2H 5 Oily matter
V-2-43 H Cl H 2，4-F 2 C 2H 5 Oily matter
V-2-44 H Cl H 3-Cl，4-F C 2H 5 Oily matter
V-2-45 H Cl H 2，5-Cl 2 C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-3) compound:
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-4) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point ℃
V-4-1 H CH 3 H 4-F C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-5) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point ℃
V-5-1 H CH 3 H 4-F C 2H 5 Oily matter
V-5-2 H CH 3 H 4-Cl C 2H 5 Oily matter
V-5-3 H Cl H 4-F C 2H 5 Oily matter
V-5-4 H Cl H 4-Cl C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-6) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point ℃
V-6-1 H CH 3 H 4-F C 2H 5 Oily matter
V-6-2 H CH 3 H 4-Cl C 2H 5 Oily matter
V-6-3 H Cl H 4-F C 2H 5 Oily matter
V-6-4 H Cl H 4-Cl C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-7) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point ℃
V-7-1 H CH 3 H 4-F C 2H 5 Oily matter
V-7-2 H CH 3 H 4-Cl C 2H 5 Oily matter
V-7-3 H Cl H 4-F C 2H 5 Oily matter
V-7-4 H Cl H 4-Cl C 2H 5 Oily matter
To be similar to the method for embodiment (V-1-1), and according to preparing the in a word bright of formula V compound, prepare with following formula (V-8) compound:
Embodiment numbering W X Y V 1/V 2 R 8 Fusing point ℃
V-8-1 H CH 3 H 4-Cl C 2H 5 33
V-8-2 H Cl H 4-Cl C 2H 5 28
embodiment (XIX-1)
The embodiment of 1.6g (6.6mmol) (X X-1) compound is dissolved in 30ml methylene dichloride, under room temperature, splashes into the solution that 1.24g (9.0mmol) oxalyl chloride is dissolved in 10ml methylene dichloride.Mixture stirring at room 12 hours, then reflux 3 hours is so that react completely.Concentrated under solution decompression.Resistates can not carry out purifying for the next step.
Productive rate: 1.6g (theoretical value 92%); Yellow oil.
To be similar to the method for embodiment (X IX-1), make with following formula (X IX) compound, wherein T=Cl:
All derivatives are with oily matter isolated in form!
Embodiment numbering W X Y V 1/V 2 δ-C H 2COCl(ppm)in CDCl 3
XIX-2 H CH 3 H 2-Cl 4.21(s)
XIX-3 H CH 3 H 3-Cl 4.22(s)
XIX-4 H CH 3 H 2-F 4.22(s)
XIX-5 H CH 3 H 3-F 4.22(s)
XIX-1 H CH 3 H 4-F 4.22(s)
XIX-6 H CH 3 H 2-CH 3 4.18(s)
XIX-7 H CH 3 H 3-CH 3 4.21(s)
XIX-8 H CH 3 H 4-CH 3 4.21(s)
XIX-9 H CH 3 H 2，3-Cl 2 4.20(s)
XIX-10 H CH 3 H 2，4-Cl 2 4.21(s)
XIX-11 H CH 3 H 2，5-Cl 2 4.21(s)
XIX-12 H CH 3 H 3，4-Cl 2 4.23(s)
XIX-13 H CH 3 H 3，5-Cl 2 4.22(s)
XIX-14 H CH 3 H 2，4-F 2 4.21(s)
XIX-15 H CH 3 H 2，5-F 2 4.21(s)
XIX-16 H CH 3 H 3-Cl，4-F 4.22(s)
XIX-17 H CH 3 H 2-CF 3 4.18(s)
XIX-18 H CH 3 H 3-CF 3 4.24(s)
XIX-19 H CH 3 H 4-CF 3 4.24(s)
XIX-20 H CH 3 H 2-OCH 3 4.18(s)
XIX-21 H CH 3 H 3-OCH 3 4.21(s)
XIX-22 H CH 3 H 4-OCH 3 4.20(s)
XIX-23 H CH 3 H 3-SO 2C 2H 5 4.25(s)
XIX-24 H CH 3 H 4-SO 2C 2H 5 4.25(s)
XIX-25 H CH 3 H 3-NO 2 4.26(s)
XIX-26 H CH 3 H 4-OCF 3 4.16(s)
Embodiment numbering W X Y V 1/V 2 δ-C H 2COCl(ppm)in CDCl 3
XIX-27 H CH 3 H 4-OPh 4.22(s)
XIX-28 H CH 3 H 4-SCH 3 4.21(s)
XIX-29 H CH 3 H 4-i-C 3H 7 4.21(s)
XIX-30 H CH 3 H 3，5-(CF 3) 2 4.27(s)
XIX-31 CH 3 CH 3 CH 3 4-F 4.26(s)
XIX-32 H CH 3 CH 3 4-Cl 4.14(s)
XIX-33 CH 3 CH 3 H 4-F 4.31(s)
XIX-34 CH 3 CH 3 H 4-Cl 4.31(s)
XIX-35 CH 3 CH 3 CH 3 4-Cl 4.26(s)
XIX-36 H Cl H 4-F 4.35(s)
XIX-37 H Cl H 4-Cl 4.34(s)
XIX-38 H Cl H 4-CF 3 4.37(s)
XIX-39 H Cl H 2，4-Cl 2 4.34(s)
XIX-40 H Cl H 3，4-Cl 2 4.36(s)
XIX-41 H Cl H 3，5-Cl 2 4.36(s)
XIX-42 H Cl H 2，4-F 2 4.35(s)
XIX-43 H Cl H 3-Cl，4-F 4.36(s)
XIX-44 H Cl H 2，5-Cl 2 4.35(s)
embodiment (X X-1)
The embodiment of 2g (7.75mmol) (XXI-6) compound is dissolved in 20ml methyl alcohol, under room temperature, adds 0.46g (11.6mmol) NaOH to be dissolved in the solution of 20ml water.Mixture stirring at room 12 hours, removes methyl alcohol under decompression, and resistates is processed in 100ml water.Methylene dichloride 3 for alkaline solution * extraction, then uses 2N hcl acidifying.Methylene dichloride 3 for acid solution * extraction, organic phase dried over sodium sulfate, filters and reduces pressure down concentrated.Sherwood oil development suction filtration for resistates.
Productive rate: 1.8g (theoretical value 95%); Colorless solid; 107 ℃ of fusing points.
To be similar to the method for embodiment (X X-1), make with following formula (X X) compound
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
XX-2 H CH 3 H 2-Cl 123
XX-3 H CH 3 H 3-Cl 136
XX-4 H CH 3 H 2-F 92
XX-5 H CH 3 H 3-F 114
XX-1 H CH 3 H 4-F 107
XX-6 H CH 3 H 2-CH 3 93
XX-7 H CH 3 H 3-CH 3 105
XX-8 H CH 3 H 4-CH 3 123
XX-9 H CH 3 H 2，3-Cl 2 158
XX-10 H CH 3 H 2，4-Cl 2 104
XX-11 H CH 3 H 2，5-Cl 2 147
XX-12 H CH 3 H 3，4-Cl 2 142
XX-13 H CH 3 H 3，5-Cl 2 175
XX-14 H CH 3 H 2，4-F 2 113
XX-15 H CH 3 H 2，5-F 2 133
XX-16 H CH 3 H 3-Cl，4-F 191
XX-17 H CH 3 H 2-CF 3 123
XX-18 H CH 3 H 3-CF 3 135
XX-19 H CH 3 H 4-CF 3 151
XX-20 H CH 3 H 2-OCH 3 88
XX-21 H CH 3 H 3-OCH 3 108
XX-22 H CH 3 H 4-OCH 3 118
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
XX-23 H CH 3 H 3-SO 2C 2H 5 142
XX-24 H CH 3 H 4-SO 2C 2H 5 154
XX-25 H CH 3 H 3-NO 2 185
XX-26 H CH 3 H 4-OCF 3 96
XX-27 H CH 3 H 4-OPh 119
XX-28 H CH 3 H 4-SCH 3 161
XX-29 H CH 3 H 4-i-C 3H 7 111
XX-30 H CH 3 H 3，5-(CF 3) 2 135
XX-31 CH 3 CH 3 CH 3 4-F 143
XX-32 H CH 3 CH 3 4-Cl 133
XX-33 CH 3 CH 3 H 4-F 158
XX-34 CH 3 CH 3 H 4-Cl 160
XX-35 H Cl H 4-F 140
XX-36 H Cl H 4-Cl 124
XX-37 H Cl H 4-CF 3 154
XX-38 H Cl H 2，4-Cl 2 110
XX-39 H Cl H 3，4-Cl 2 182
XX-40 H Cl H 3，5-Cl 2 154
XX-41 H Cl H 2，4-F 2 145
XX-42 H Cl H 3-Cl，4-F 228
XX-43 H Cl H 2，5-Cl 2 171
XX-44 CH 3 CH 3 CH 3 4-Cl 165
embodiment (X XI-1)
First by 14.8g (61mmol) bbe added in 70ml glycol dimethyl ether, under the logical argon gas condition of room temperature, add successively 56ml 1 volumetric molar concentration sodium carbonate solution, a(12.4g; 80mmol) and two (triphenyl phosphine) Palladous chloride (II) of catalytic amount.At 80 ℃, mixture, heat 12 hours, be then cooled to room temperature, add 150ml water, ethyl acetate 3 for mixture * extraction.Organic phase dried over sodium sulfate, filters, and decompression is lower to desolventizing.
Productive rate: 16.7g (quantitatively); Brown color oily matter, purifying is not synthetic for lower step.
To be similar to the method for embodiment (X X-1), make with following formula (X XI) compound, wherein R 8=CH 3:
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
XXI-2 H CH 3 H 2-Cl Oily matter
XXI-3 H CH 3 H 3-Cl Oily matter
XXI-4 H CH 3 H 2-F Oily matter
XXI-5 H CH 3 H 3-F Oily matter
XXI-6 H CH 3 H 4-F Oily matter
XXI-7 H CH 3 H 2-CH 3 Oily matter
XXI-8 H CH 3 H 3-CH 3 Oily matter
XXI-9 H CH 3 H 4-CH 3 Oily matter
XXI-10 H CH 3 H 2，3-Cl 2 Oily matter
XXI-11 H CH 3 H 2，4-Cl 2 Oily matter
XXI-12 H CH 3 H 2，5-Cl 2 Oily matter
XXI-13 H CH 3 H 3，4-Cl 2 Oily matter
XXI-14 H CH 3 H 3，5-Cl 2 Oily matter
XXI-15 H CH 3 H 2，4-F 2 Oily matter
Embodiment numbering W X Y V 1/V 2 Fusing point (℃)
XXI-16 H CH 3 H 2，5-F 2 Oily matter
XXI-17 H CH 3 H 3-Cl，4-F Oily matter
XXI-18 H CH 3 H 2-CF 2 Oily matter
XXI-19 H CH 3 H 3-CF 3 Oily matter
XXI-20 H CH 3 H 4-CF 3 Oily matter
XXI-21 H CH 3 H 2-OCH 3 Oily matter
XXI-22 H CH 3 H 3-OCH 3 Oily matter
XXI-23 H CH 3 H 4-OCH 3 64
XXI-24 H CH 3 H 3-SO 2C 2H 5 Oily matter
XXI-25 H CH 3 H 4-SO 2C 2H 5 89
XXI-26 H CH 3 H 3-NO 2 Oily matter
XXI-27 H CH 3 H 4-OCF 3 Oily matter
XXI-28 H CH 3 H 4-OPh Oily matter
XXI-29 H CH 3 H 4-SCH 3 92
XXI-30 H CH 3 H 4-i-C 3H 7 Oily matter
XXI-31 H CH 3 H 3，5-(CF 3) 2 63
XXI-32 CH 3 CH 3 CH 3 4-F Oily matter
XXI-33 H Cl H 4-F Oily matter
XXI-34 H Cl H 4-CF 3 Oily matter
XXI-35 H CH 3 CH 3 4-Cl Oily matter
XXI-36 CH 3 CH 3 H 4-F Oily matter
XXI-37 CH 3 CH 3 H 4-Cl Oily matter
XXI-38 CH 3 CH 3 CH 3 4-Cl Oily matter
XXI-39 H Cl H 4-Cl Oily matter
XXI-40 H Cl H 2，4-Cl 2 Oily matter
XXI-41 H Cl H 3，4-Cl 2 Oily matter
XXI-42 H Cl H 3，5-Cl 2 Oily matter
XXI-43 H Cl H 2，4-F 2 Oily matter
XXI-44 H Cl H 3-Cl-4-F Oily matter
XXI-45 H Cl H 2，5-Cl 2 Oily matter
purposes embodiment
embodiment A
Horseradish daikon leaf beetle test (spray and process)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
Chinese cabbage (Brassica perkinensis) leaf sprays with the active agent preparations of desired concn, dry rear access horseradish daikon leaf beetle (Phaedon cochleariae) larva.
After required time, determine % activity ratio.100% represents to kill all larvas; 0% indicates to kill without larva.
In this test, for example the compound of following Preparation Example is very effective:
table A
The insect of harm plant
The test of horseradish daikon leaf beetle
Active compound Activity compound concentration g/ha Killing rate % after 7 days
Example I-1-a-4 500 100
embodiment B
Meadow mythimna separata test (spray and process)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
Corn (Zea mays) leaf sprays with the active agent preparations of desired concn, dry rear access meadow mythimna separata (Spodoptera frugiperda) Candle-sticks.
After required time, determine % activity ratio.100% represents to kill all Candle-sticks; 0% indicates to kill without Candle-sticks.
In this test, for example the compound of following Preparation Example is very effective:
table B
The insect of harm plant
Meadow mythimna separata test
Active compound Activity compound concentration g/ha Killing rate % after 7 days
Example I-1-b-4 500 100
Example I-1-c-4 500 100
embodiment C
The test of jute root nodule nematode
Solvent: the dimethyl formamide of 7 weight parts
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount, and dope is diluted with water to desired concn.
Sand, active compounds solution, jute root nodule nematode (Meloidogyne incognita) ovum/larva suspension and head lettuce seed filling for container.Head lettuce seed germination, plant-growth.At root, form insect gall.
After required time, by the gall formation rate representing with %, determine nematicide drug effect.100% represents not find insect gall; Insect gall amount on 0% plant that represents to process equates with untreated control sample.
In this test, for example the compound of following Preparation Example is very effective:
table C
The nematode of harm plant
The test of jute root nodule nematode
Active compound Activity compound concentration ppm Drug effect % after 14 days
Example I-1-a-1 20 80
Example I-1-b-1 20 90
Example I-2-c-6 20 90
embodiment D
Black peach aphid test (spray and process)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
The Chinese cabbage leaf that will be infected by each stage black peach aphid (Myzus persicae) sprays with the active agent preparations of desired concn.
After required time, determine % activity ratio.100% represents to kill all black peach aphids; 0% indicates to kill without black peach aphid.
In this test, for example the compound of following Preparation Example is very effective:
table D
The insect of harm plant
Black peach aphid test
Active compound Activity compound concentration g/ha Killing rate % after 5 days
Example I-2-c-6 100 100
Example I-1-c-1 100 100
Example I-1-b-33 100 100
Example I-2-a-32 500 90
Example I-1-b-11 500 100
Example I-1-c-15 500 100
Example I-1-b-14 500 100
Example I-2-b-15 500 100
Example I-2-c-16 500 100
Example I-1-b-17 500 90
Example I-2-b-21 500 100
Example I-1-b-26 500 100
Example I-2-b-13 500 100
Example I-1-b-30 500 100
Example I-2-b-31 500 100
Example I-2-b-30 500 100
embodiment E
Horseradish daikon leaf beetle test (spray and process)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
Chinese cabbage leaf sprays with the active agent preparations of desired concn, dry rear access horseradish daikon leaf beetle (Phaedon cochleariae) larva.
After required time, determine % activity ratio.100% represents to kill all larvas; 0% indicates to kill without larva.
In this test, for example the compound of following Preparation Example is very effective:
table E
The insect of harm plant
The test of horseradish daikon leaf beetle
Active compound Activity compound concentration g/ha Killing rate % after 7 days
Example I-1-b-1 500 100
Example I-1-c-1 100 100
Example I-1-a-13 500 100
Example I-2-a-13 500 100
Example I-1-b-4 500 100
Example I-1-b-13 500 100
Example I-1-c-15 500 100
Example I-2-c-4 500 100
Example I-2-c-7 500 100
Example I-1-c-9 500 100
Example I-1-c-14 500 100
Example I-1-b-16 500 100
Example I-2-c-12 500 100
Example I-2-c-9 500 100
Example I-2-c-11 500 100
Example I-1-b-27 500 100
Example I-2-a-26 500 100
Example I-2-c-14 500 100
Example I-2-c-15 500 100
Example I-2-b-17 500 100
Example I-2-c-17 500 100
Example I-2-b-19 500 100
Example I-2-c-19 500 100
Example I-2-b-32 500 100
embodiment F
Meadow mythimna separata test (spray and process)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
Corn (Zea mays) leaf sprays with the active agent preparations of desired concn, dry rear access meadow mythimna separata (Spodoptera frugiperda) Candle-sticks.
After required time, determine % activity ratio.100% represents to kill all Candle-sticks; 0% indicates to kill without Candle-sticks.
In this test, for example the compound of following Preparation Example is very effective:
table F
The insect of harm plant
Meadow mythimna separata test
Active compound Activity compound concentration g/ha Killing rate % after 7 days
Example I-2-a-6 500 100
Example I-1-b-11 500 100
Example I-1-c-13 500 83
Example I-1-b-15 500 100
Example I-2-b-3 500 83
Example I-2-c-3 500 100
Example I-2-b-5 500 100
Example I-2-c-5 500 100
Example I-2-b-15 500 100
Example I-1-b-17 500 100
Example I-1-c-17 500 83
Example I-2-b-20 500 100
Example I-2-c-20 500 100
Example I-1-c-18 500 100
Example I-2-b-2 500 100
Example I-2-c-2 500 83
Example I-2-c-13 500 100
Example I-1-b-32 100 100
embodiment G
T.urticae Koch test (OP-resistance/sprinkling is processed)
Solvent: the acetone of 78 weight parts
The dimethyl formamide of 1.5 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 0.5 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted to desired concn with the water that contains emulsifying agent.
String bean (Phaseolus vulgaris) leaf that will be infected by each stage T.urticae Koch (Tetranychus urticae) sprays with the active agent preparations of desired concn.
After required time, determine % activity ratio.100% represents to kill all tetranychids; 0% indicates to kill without tetranychid.
In this test, for example the compound of following Preparation Example is very effective:
table G
The acarid of harm plant
T.urticae Koch test (OP-resistance/sprinkling is processed)
Active compound Activity compound concentration g/ha Killing rate % after 5 days
Example I-2-b-6 100 90
Example I-1-a-10 500 90
Example I-3-a-1 100 90
Example I-1-a-11 500 100
Example I-1-b-4 500 100
Example I-1-c-7 500 100
Example I-1-c-11 500 100
Example I-1-c-12 500 100
Example I-1-c-15 500 100
Example I-2-c-23 500 100
Example I-1-b-9 500 100
Example I-1-c-16 500 100
Example I-2-b-10 500 100
Example I-2-c-10 500 100
Example I-1-b-28 500 100
Example I-1-a-17 500 90
Example I-2-a-2 500 90
Example I-1-c-17 500 100
Example I-1-b-10 500 90
Example I-2-c-26 100 90
Example I-3-b-1 500 90
Example I-1-b-34 500 90
embodiment H
Single softgel shell test (cucumber)/protectiveness
Solvent: the DMF of 49 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount and emulsifying agent, and dope is diluted with water to desired concn.
For test prolection, the cucumber plant of childhood is sprayed with described rate of application with active agent preparations.Process after 1 day the inoculation of the spore suspension of Flower of Garden Balsam list softgel shell for described plant (Sphaerotheca fuliginea).Then plant is put into the greenhouse of 23 ℃ of relative atmospheric moistures 70%, temperature.
Cultivate and evaluate and test after 7 days.0% represents that drug effect equates with control sample, and 100% drug effect represents not observe and infects.
table H
Single softgel shell test (cucumber)/protectiveness
Active compound Active compound rate of application g/ha Drug effect %
Example I-1-b-1 750 94
Example I-1-b-3 750 90
Example I-1-c-1 750 80
example I
In vitro tests is to determine the ED to microorganism 50
In the hole of microtiter plate, with transfer pipet, add the methanol solution of the active compound to be measured mixing with emulsifying agent PS16.After solvent evaporation, in each hole, add 200 μ l potato/glucose substratum.
The spore or the mycelium that in substratum, add in advance the fungi to be measured that is applicable to concentration.
Gained activity compound concentration is 0.1,1,10 and 100ppm.Gained emulsifier concentration is 300ppm.
Then by titer plate 22 ℃ of cultivation 3-5 days on rocker, until can observe enough growths in untreated control sample.
Evaluation and test is carried out at 620nm wavelength place with spectrophotometry.By the take off data under different concns, calculate the fungal growth inhibiting rate of sening as an envoy to and with respect to untreated control sample, reach 50% active compound doses (ED 50).
table I
In vitro tests is to determine the ED to microorganism 50
Active compound Microorganism ED 50Value
Example I-2-b-6 Hidden ground epidemic disease mould (Phytophthora cryptogea) 0.56
Example I-2-c-6 Hidden ground epidemic disease is mould 1.04
Example I-1-c-1 Hidden ground epidemic disease is mould 0.71
embodiment J
Herbicide effect after emerging
The seed of unifacial leaf and dicots weeds and farm crop is inserted in the sandy loam in xylon basin, with soil, cover, and under better growing conditions, cultivate in greenhouse.2-3 is after week in sowing, processes the test plant of 1 leaf phase.To wherein add the test compound of wettable powder (WP) formulation of 0.2% wetting agent with various dose, to be sprayed on the green parts of plant, wherein water rate of application be 600 1/ha (after conversions).Test plant in greenhouse under optimal growth condition after approximately 3 weeks, with the comparison of untreated control sample, the drug effect of visual assessment preparation (per-cent weeding drug effect (%): 100% drug effect=plant is dead, 0% drug effect=with control sample plant).
embodiment K
Threshold concentration test/soil insect-transgenic plant are processed
Test insect: larva in cucumber strip chrysomelid (Diabrotica balteata)-soil
Solvent: the acetone of 7 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
For preparing applicable active agent preparations, mix the active compound of 1 weight part and the solvent of described amount, add the emulsifying agent of described amount, and dope is diluted with water to desired concn.
Active agent preparations is poured onto on soil.Herein, the activity compound concentration in preparation is unimportant, and key is the active compound weight of per unit volume soil, with ppm (mg/l), explains.Soil is inserted in 0.251 basin, standing at 20 ℃.
After described preparation process, immediately 5 corn (maize corn) cultivar YIELD GUARD (U.S. Meng Shan is (Monsanto) company logo) that vernalization has been processed are inserted in each basin.After 2 days, suitable test insect is inserted in the soil of processed mistake.After 7 days, the maize plant number of having emerged by statistics is determined active compound drug effect (1 strain plant=20% activity ratio).
embodiment L
Cigarette bud-leaf moth test-transgenic plant are processed
Solvent: the acetone of 7 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
For preparing applicable active agent preparations, mix the emulsifying agent of the active compound of 1 weight part and the solvent of described amount and described amount, and dope is diluted with water to desired concn.
By in the active agent preparations of soya bean seedling (Glycine max) cultivar Roundup Ready (About Monsanto Chemicals's trade mark) immersion desired concn, it being processed, when leaf is still moistening, access cigarette bud-leaf moth (Heliothis virescens).
After required time, determine that insect kills.

Claims (9)

1. formula (X IX) compound
Wherein
X represents halogen,
W and Y represent hydrogen or C independently of one another 1-C 6alkyl,
One of following group of Z representative
V 1represent halogen, C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, halogen or C 1-C 4haloalkyl,
V 3represent hydrogen;
Or
X represents halogen or C 1-C 6alkyl,
W represents C 1-C 6alkyl,
Y represents hydrogen or C 1-C 6alkyl,
One of following group of Z representative
V 1represent halogen, C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, halogen or C 1-C 4haloalkyl,
V 3represent hydrogen;
Or
X represents halogen or C 1-C 6alkyl,
W represents hydrogen or C 1-C 6alkyl,
Y representative has the alkyl of 1 carbon atom to 6 carbon atom, gets rid of the alkyl with 1 carbon atom,
One of following group of Z representative
V 1represent halogen, C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, halogen or C 1-C 4haloalkyl,
V 3represent hydrogen;
Or
X represents halogen or C 1-C 6alkyl,
W and Y represent hydrogen or C independently of one another 1-C 6alkyl,
One of following group of Z representative
V 1represent C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, halogen or C 1-C 4haloalkyl,
V 3represent hydrogen;
Or
X represents halogen or C 1-C 6alkyl,
W and Y represent hydrogen or C independently of one another 1-C 6alkyl,
One of following group of Z representative
V 1represent halogen, C 1-C 12alkyl, C 1-C 6alkoxyl group, C 1-C 6alkylthio, C 1-C 6alkyl sulphonyl, C 1-C 4haloalkyl, C 1-C 4halogenated alkoxy, nitro or phenoxy group,
V 2represent halogen or C 1-C 4haloalkyl,
V 3represent hydrogen;
T representative is by the leavings group of reagent place's introducing of activating carboxy acid, and wherein said reagent is halogenating agent,
Get rid of following compound
2. the compound of claim 1, wherein said reagent is thionyl chloride, oxalyl chloride, carbonyl chloride, SULPHURYL CHLORIDE or chloro-formic ester.
3. the compound of claim 1, wherein said reagent is toluene sulfonyl chloride.
4. the compound of one of claim 1-3, wherein
W represents hydrogen, methyl or ethyl,
X represents fluorine, chlorine or bromine,
Y represents hydrogen or C 1-C 4alkyl,
V 1represent fluorine, chlorine, bromine, C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, fluorine, chlorine, bromine or C 1-C 2haloalkyl;
Or
W represent methylidene or ethyl,
X represents fluorine, chlorine, bromine or C 1-C 4alkyl,
Y represents hydrogen or C 1-C 4alkyl,
V 1represent fluorine, chlorine, bromine, C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, fluorine, chlorine, bromine or C 1-C 2haloalkyl;
Or
W represents hydrogen, methyl or ethyl,
X represents fluorine, chlorine, bromine or C 1-C 4alkyl,
Y representative has the alkyl of 1 carbon atom to 4 carbon atom, gets rid of the alkyl with 1 carbon atom,
V 1represent fluorine, chlorine, bromine, C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, fluorine, chlorine, bromine or C 1-C 2haloalkyl;
Or
W represents hydrogen, methyl or ethyl,
X represents fluorine, chlorine, bromine or C 1-C 4alkyl,
Y represents hydrogen or C 1-C 4alkyl,
V 1represent C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or phenoxy group,
V 2represent hydrogen, fluorine, chlorine, bromine or C 1-C 2haloalkyl;
Or
W represents hydrogen, methyl or ethyl,
X represents fluorine, chlorine, bromine or C 1-C 4alkyl,
Y represents hydrogen or C 1-C 4alkyl,
V 1represent fluorine, chlorine, bromine, C 1-C 6alkyl, C 1-C 4alkoxyl group, C 1-C 4alkylthio, C 1-C 4alkyl sulphonyl, C 1-C 2haloalkyl, C 1-C 2halogenated alkoxy, nitro or phenoxy group,
V 2represent fluorine, chlorine, bromine or C 1-C 2haloalkyl.
5. the compound of one of claim 1-3, wherein
W represents hydrogen, methyl or ethyl,
X represents chlorine,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represent methylidene or ethyl,
X represents chlorine, methyl, ethyl or propyl group,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represents hydrogen, methyl or ethyl,
X represents chlorine, methyl, ethyl or propyl group,
Y represents hydrogen or methyl,
V 1represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represents hydrogen, methyl or ethyl,
X represents chlorine, methyl, ethyl or propyl group,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, bromine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent fluorine, chlorine or trifluoromethyl.
6. the compound of one of claim 1-3, wherein
W represents hydrogen or methyl,
X represents chlorine,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, methyl, sec.-propyl, methoxyl group, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represent methylidene,
X represents chlorine or methyl,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, methyl, sec.-propyl, methoxyl group, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represents hydrogen or methyl,
X represents chlorine or methyl,
Y represents hydrogen or methyl,
V 1represent methylidene, sec.-propyl, methoxyl group, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent hydrogen, fluorine, chlorine or trifluoromethyl;
Or
W represents hydrogen or methyl,
X represents chlorine or methyl,
Y represents hydrogen or methyl,
V 1represent fluorine, chlorine, methyl, sec.-propyl, methoxyl group, trifluoromethyl, trifluoromethoxy, SO 2c 2h 5, SCH 3, phenoxy group or nitro,
V 2represent fluorine, chlorine or trifluoromethyl.
7. the compound of one of claim 1-3, wherein
Z represents following group
T represents chlorine,
And W, X, Y, V 1and V 2there is following implication
W X Y V1/V2 H CH 3 H 2-Cl H CH 3 H 3-Cl H CH 3 H 2-F H CH 3 H 3-F H CH 3 H 4-F
H CH 3 H 2-CH 3 H CH 3 H 3-CH 3 H CH 3 H 4-CH 3 H CH 3 H 2,3-Cl 2 H CH 3 H 2,4-Cl 2 H CH 3 H 2，5-Cl 2 H CH 3 H 3，4-Cl 2 H CH 3 H 3，5-Cl 2 H CH 3, H 2，4-F 2 H CH 3 H 2，5-F 2 H CH 3 H 3-Cl,4-F H CH 3 H 2-CF 3 H CH 3 H 3-CF 3 H CH 3 H 4-CF 3 H CH 3 H 2-OCH 3 H CH 3 H 3-OCH 3, H CH 3 H 4-OCH 3 H CH 3 H 3-SO 2C 2H 5 H CH 3 H 4-SO 2C 2H 5 H CH 3 H 3-NO 2 H CH 3 H 4-OCF 3 H CH 3 H 4-OPh H CH 3 H 4-SCH 3 H CH 3 H 4-i-C 3H 7 H CH 3 H |3，5-(CF 3) 2 CH 3 CH 3 CH 3 4-F H CH 3 CH 3 4-Cl CH 3 CH 3 H 4-F CH 3 CH 3 H 4-Cl H Cl H 4-F H Cl H 4-Cl H Cl H 4-CF 3 H Cl H 2，4-Cl 2 H Cl H 3，4-Cl 2 H Cl H 3，5-Cl 2 H Cl H 2，4-F 2 H Cl H 3-Cl，4-F， H Cl H 2，5-Cl 2
。
8. formula (XX) compound
Wherein
W, X, Y and Z definition, as any one of claim 1-7, are got rid of following compound
9. formula (X XI) compound
Wherein
W, X, Y and Z definition are as any one of claim 1-7, R 8represent C 1-C 8alkyl, gets rid of following compound
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